Thermoplastic foam article

Abstract

The present application relates to thermoplastic foam articles. Various foams and foam components are provided, including foam components for articles of footwear and articles of athletic equipment. The articles include a composition having a foam structure, wherein the composition comprises a thermoplastic copolyester elastomer comprising: (a) a plurality of first segments, each first segment derived from a dihydroxyl-terminated polydiol; (b) a plurality of second segments, each second segment derived from a diol; and (c) a plurality of third segments, each third segment derived from an aromatic dicarboxylic acid. Methods of making the composition and the foam are provided, as well as methods of making an article of footwear comprising at least one of the foam components. In some aspects, the foams and foam components can be manufactured by extrusion or injection molding to foam the polymeric composition, or by extrusion or injection molding to foam the polymeric composition followed by compression molding of the foam.

Description

[0001] This application is a divisional application of the application filed on March 12, 2019, with application number 201980030027.6 and invention title "Thermoplastic Foam Articles".

[0002] Cross-reference to related applications

[0003] This application claims the benefits of U.S. Provisional Application No. 62 / 641,701, filed March 12, 2018, and U.S. Provisional Application No. 62 / 645,036, filed March 19, 2018, each of which is incorporated herein by reference in its entirety. Technical Field

[0004] This disclosure generally relates to foams formed from thermoplastic copolyester elastomers, and particularly to foams formed from thermoplastic copolyester elastomers suitable for footwear and related industries, and their uses. background

[0005] The design of sports equipment, apparel, and footwear involves a wide range of factors, from aesthetics and comfort to performance and durability. While designs and fashions can change rapidly, the market demand for enhanced performance remains constant. To balance these needs, designers utilize a variety of materials and designs for the various components that make up sports equipment, apparel, and footwear. Summary of the Invention

[0006] This application provides the following:

[0007] 1) A thermoplastic foam article, comprising:

[0008] A foamed polymer material, the foamed polymer material comprising a thermoplastic copolyester elastomer, wherein the thermoplastic copolyester elastomer comprises:

[0009] (a) More than one first segment, each first segment being derived from a dihydroxy-terminated polydiol;

[0010] (b) More than one second segment, each second segment derived from a diol; and

[0011] (c) More than one third segment, each of which is derived from an aromatic dicarboxylic acid;

[0012] The thermoplastic foam article described therein has a porous foam structure.

[0013] 2) The thermoplastic foam article according to claim 1), wherein the thermoplastic copolyester elastomer comprises:

[0014] (a) More than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polyethylene glycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0015]

[0016] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and

[0017] (b) More than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0018]

[0019] Wherein R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0020] 3) The thermoplastic foam article according to 2), wherein the first copolyester unit has a structure represented by Formula 3:

[0021]

[0022] Wherein R is H or methyl; where y is an integer having a value from 1 to 10; where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons.

[0023] 4) The thermoplastic foam article according to 3), wherein y is an integer having a value of 1, 2, 3, 4 or 5.

[0024] 5) The thermoplastic foam article according to 3), wherein y is an integer having a value of 1, 2 or 3.

[0025] 6) The thermoplastic foam article according to 3), wherein R is hydrogen.

[0026] 7) The thermoplastic foam article according to 3), wherein R is methyl.

[0027] 8) The thermoplastic foam article according to 3), wherein R is hydrogen and y is an integer having a value of 1, 2 or 3.

[0028] 9) The thermoplastic foam article according to 3), wherein R is methyl and y is an integer having a value of 1.

[0029] 10) The thermoplastic foam article according to 2), wherein the first copolyester unit has a structure represented by Formula 4:

[0030]

[0031] Where z is an integer having a value from 2 to 60; and the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons.

[0032] 11) The thermoplastic foam article according to 10), wherein z is an integer having a value from 5 to 60.

[0033] 12) The thermoplastic foam article according to 10), wherein the weight-average molecular weight of each of the more than one first copolyester unit is from about 400 Daltons to about 6,000 Daltons.

[0034] 13) The thermoplastic foam article according to 2), wherein the second copolyester unit has a structure represented by Formula 5:

[0035]

[0036] Where x is an integer with values ​​from 1 to 20.

[0037] 14) The thermoplastic foam article according to 13), wherein x is an integer having a value from 2 to 18.

[0038] 15) The thermoplastic foam article according to 2), wherein the thermoplastic copolyester elastomer comprises the more than one first copolyester unit based on about 30% to about 80% by weight of the total weight of the thermoplastic copolyester elastomer.

[0039] 16) The thermoplastic foam article according to 2), wherein the thermoplastic copolyester elastomer comprises the more than one second copolyester unit based on about 40% to about 65% by weight of the total weight of the thermoplastic copolyester elastomer.

[0040] 17). The thermoplastic foam article according to 1), wherein the porous foam structure is an open-cell foam structure.

[0041] 18) The thermoplastic foam article according to 1), wherein the foam article has a specific gravity from about 0.08 to about 0.31.

[0042] 19) The thermoplastic foam article according to 1), wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of about 50,000 Daltons to about 1,000,000 Daltons.

[0043] 20) The thermoplastic foam article according to 1), wherein the thermoplastic copolyester elastomer has a ratio of the first segment to the third segment of about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment; or wherein the thermoplastic copolyester elastomer has a ratio of the second segment to the third segment of about 1:1 to about 1:3 based on the weight of each of the second segment and the third segment. Attached Figure Description

[0044] Other aspects of this disclosure will be readily understood when viewed in conjunction with the accompanying drawings and after reviewing the detailed description described below.

[0045] Figure 1 This is a front view of a footwear article having a sole component according to one aspect of the present invention.

[0046] Figure 2 yes Figure 1 An exploded view of the sole component of footwear.

[0047] Figure 3 yes Figure 1 A plan view of the bottom of the sole component of footwear.

[0048] Figure 4 This is a bottom view of the insert for the sole component of footwear.

[0049] Figure 5 It is inserted into the first part to form the sole component. Figure 4 Top view of the insert.

[0050] Figure 6 Representative compression data are shown for a representative foam plaque comprising the disclosed composition and prepared using the disclosed method.

[0051] Figure 7 A representative schematic diagram illustrating the disclosed method for determining peak and tail temperatures is shown.

[0052] Figures 8A-8D Representative images of cross-sectional views of foam substrates prepared using the disclosed thermoplastic copolyester elastomer at different temperatures are shown. Each image shows a scalar bar (500 micrometers). The foam substrates were prepared at the following temperatures: 175°C ( Figure 8A ); 190℃ Figure 8B ); 205℃ Figure 8C ); and 245℃ ( Figure 8D ).

[0053] Figure 9 A representative image of a cross-sectional view of a foam substrate prepared using the disclosed thermoplastic copolyester elastomer at 160°C is shown. The image shows a scale bar (500 micrometers). Detailed description

[0054] This disclosure relates to foams comprising thermoplastic copolyester elastomers, specifically thermoplastic copolyester elastomer foams. Thermoplastic copolyester elastomer foams are formed from polymer compositions comprising one or more thermoplastic copolyester elastomers. Examples of thermoplastic copolyester elastomers include polymers having one or more carboxylic acid moieties present in the polymer backbone, on one or more side chains, or both in the polymer backbone and on one or more side chains. The one or more carboxylic acid moieties of the thermoplastic copolyester elastomer may include free carboxylic acid, salts of carboxylic acids, or anhydrides of carboxylic acids. In specific examples, the carboxylic acid moieties may be acrylic acid moieties or methacrylic acid moieties. The thermoplastic copolyester elastomer foams of this disclosure are suitable for use in a variety of articles. Thermoplastic copolyester elastomer foams are particularly suitable for sports equipment and apparel, especially footwear (e.g., midsoles / outsoles of athletic footwear). As discussed below, thermoplastic copolyester elastomer foams exhibit a unique balance of properties such as high energy return, high split tear, low density, and low compression set. Unlike thermosetting polymer compositions and foaming methods that form thermosetting foams, the thermoplastic compositions and foaming methods described herein do not require the formation of irreversible chemical bonds (e.g., crosslinking bonds) during the foaming process, and therefore the cured foams described herein retain the thermoplastic properties of the copolyester elastomer. In some instances, the level of crosslinks between thermoplastic copolyester elastomer chains is low before foaming and remains substantially unchanged after the foam has cured. The thermoplastic copolyester elastomer foams described herein can be repeatedly melted and reprocessed (e.g., for recycling) with minimal loss of physical properties, providing a solution for material sustainability.

[0055] In a first aspect, this disclosure relates to foam articles comprising: a foamed polymer material comprising a thermoplastic copolyester elastomer, wherein the thermoplastic copolyester elastomer comprises: (a) more than one first segment, each first segment derived from a dihydroxy-terminated polydiol; (b) more than one second segment, each second segment derived from a diol; and (c) more than one third segment, each third segment derived from an aromatic dicarboxylic acid; wherein the foam article has a microporous foam structure. The thermoplastic copolyester elastomer of the foam article may be substantially uncrosslinked. In one example, the microporous foam structure is a closed-cell microporous foam structure. In another example, the microporous foam structure is an open-cell microporous foam structure.

[0056] In a second aspect, this disclosure relates to foam articles comprising: a foamed polymer material comprising a thermoplastic copolyester elastomer, wherein the thermoplastic copolyester elastomer comprises: (a) more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0057]

[0058] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and (b) more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0059]

[0060] R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; wherein the foam article has a microporous foam structure. In one example, the thermoplastic copolyester elastomer of the foam article is substantially uncrosslinked.

[0061] In a third aspect, this disclosure relates to foam articles comprising: a foamed polymer material comprising a thermoplastic copolyester elastomer, wherein the thermoplastic copolyester elastomer comprises: (a) more than one first copolyester unit, each of the more than one first copolyester unit having a structure represented by Formula 4:

[0062]

[0063] Where z is an integer having a value from 2 to 60; and wherein the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons; and (b) more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0064]

[0065] Where x is an integer having a value from 1 to 20; and where the foam article has a microporous foam structure. In one example, the thermoplastic copolyester elastomer of the foam article is substantially uncrosslinked.

[0066] In a fourth aspect, this disclosure relates to a method for manufacturing a foam article, the method comprising: forming a mixture of a molten polymer material and a blowing agent, wherein the polymer material comprises a thermoplastic copolyester elastomer having: (a) more than one first segment, each first segment derived from a dihydroxy-terminated polydiol; (b) more than one second segment, each second segment derived from a diol; and (c) more than one third segment, each third segment derived from an aromatic dicarboxylic acid; injecting the mixture into a mold cavity; foaming the molten polymer material while reducing the temperature or pressure of the molten polymer material, or both, thereby forming a foam article having a microporous foam structure; curing the foam; and removing the cured foam article from the mold cavity. In one example, the crosslinking density of the thermoplastic copolyester elastomer remains substantially unchanged in the cured foam article compared to the molten polymer material. The blowing agent may be a physical blowing agent such as supercritical nitrogen or supercritical carbon dioxide, or it may be a chemical blowing agent.

[0067] In a fifth aspect, this disclosure relates to a method for manufacturing foam articles, the method comprising: forming a mixture of a molten polymer material and a foaming agent, wherein the polymer material comprises a thermoplastic copolyester elastomer having: (a) more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0068]

[0069] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and (b) more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0070]

[0071] R3 is the group remaining after removing the hydroxyl group from a diol derived from the second segment of the diol, wherein the diol is a diol with a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from an aromatic dicarboxylic acid from the third segment; the mixture is injected into a mold cavity; the molten polymer material is foamed while the temperature or pressure of the molten polymer material, or both, is reduced, thereby forming a foam article with a microporous foam structure; the foam is cured; and the cured foam article is removed from the mold cavity. In one example, the crosslinking density of the thermoplastic copolyester elastomer remains substantially unchanged in the cured foam article compared to the molten polymer material. The foaming agent can be a physical foaming agent such as supercritical nitrogen or supercritical carbon dioxide, or it can be a chemical foaming agent.

[0072] In a sixth aspect, this disclosure relates to a method for manufacturing foam articles, the method comprising: forming a mixture of a molten polymer material and a foaming agent, wherein the polymer material comprises a thermoplastic copolyester elastomer having: (a) more than one first copolyester unit, each of the more than one first copolyester unit having a structure represented by Formula 4:

[0073]

[0074] Where z is an integer having a value from 2 to 60; and wherein the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons; and (b) more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0075]

[0076] Where x is an integer having a value from 1 to 20; where the foam article has a microporous foam structure; the mixture is injected into a mold cavity; the molten polymer material is foamed while the temperature or pressure of the molten polymer material, or both, is reduced, thereby forming a foam article with a microporous foam structure; and the foam article is removed from the mold cavity. In one example, the crosslinking density of the thermoplastic copolyester elastomer remains substantially constant in the cured foam article compared to the molten polymer material. The foaming agent can be a physical foaming agent such as supercritical nitrogen or supercritical carbon dioxide, or it can be a chemical foaming agent.

[0077] In a seventh aspect, this disclosure relates to a method for manufacturing footwear articles, the method comprising: attaching a foam article and a textile element to each other; wherein the foam article is any disclosed foam article.

[0078] In the eighth aspect, this disclosure relates to a method for manufacturing footwear articles, the method comprising: attaching foam articles and textile elements to each other; wherein the foam articles are manufactured by any of the disclosed methods.

[0079] In the ninth aspect, this disclosure relates to items including any publicly disclosed foam articles.

[0080] In the tenth aspect, this disclosure relates to articles, including foam articles manufactured by any disclosed method.

[0081] Items manufactured using the disclosed methods.

[0082] Footwear 10 is an exemplary athletic footwear article comprising the thermoplastic copolyester elastomer foam described herein. Although illustrated as a running shoe, footwear 10 can be optionally configured for any suitable athletic performance, such as baseball shoes, basketball shoes, soccer shoes, American football shoes, running shoes, cross-training shoes, cheerleading shoes, golf shoes, and the like. While athletic shoes are... Figure 1 The examples are illustrated herein, but it will be readily understood that some of the terminology used will also apply to other footwear items or to other styles of shoes. Footwear 10 includes an upper 12 and a sole component 14 attached to the upper 12. The sole component 14 may be attached to the upper 12 by adhesive or any other suitable means. As used herein, the sole component 14 may be a monolithic component formed entirely of a thermoplastic copolyester elastomer foam material as described herein, or a multi-component assembly formed of more than one monolithic component, wherein at least one of the monolithic components is formed entirely of a thermoplastic copolyester elastomer foam material as described herein.

[0083] Footwear 10 has an inner or medial side 16 and an outer or lateral side 18. For ease of discussion, footwear 10 can be divided into three parts: a forefoot portion 20, a midfoot portion 22, and a heel portion 24. Parts 20, 22, and 24 are not intended to precisely delineate the areas of footwear 10. Rather, parts 20, 22, and 24 are intended to represent the various areas of footwear 10, which provides a frame of reference during the discussion below. Unless otherwise indicated, directional terms used herein, such as backward, forward, top, bottom, inward, downward, upward, etc., refer to directions relative to footwear 10 itself. Footwear 10 in Figure 1 The orientation is generally horizontal, as if it would be positioned on a horizontal surface when worn by the wearer. However, it should be understood that footwear 10 does not need to be restricted to such an orientation. Therefore, in Figure 1 In the middle, towards the back is the part facing the heel 24 (e.g.) Figure 1 (As seen in the image, to the right), forward is towards the front part of the shoe (e.g., 20). Figure 1 (As seen in the image, to the left), and downwards is towards... Figure 1 The bottom of the page as seen in the image. The top refers to the area facing upwards. Figure 1 The element at the top of the view, while the bottom refers to the element facing the top. Figure 1 The element at the bottom of the view. Inward is towards the center of footwear 10, and outward is towards the outer edge of footwear 10.

[0084] In some aspects, the component is the sole component, such as... Figures 1-5 The sole component 14 depicted herein comprises the thermoplastic copolyester elastomer foam described herein. In some aspects, the component is an insert, such as... Figures 4-5The insert 36 or 60 depicted herein comprises the thermoplastic copolyester elastomer foam described herein. The sole component and the insert for the sole component may be partially or entirely made of the thermoplastic copolyester elastomer foam described herein. Any portion of the sole component or the insert for the sole component may be made of the thermoplastic copolyester elastomer foam described herein. For example, a first portion 26 of the sole component (optionally including a lower surface 44 engaging the ground, such as more than one protrusion 46 and / or a groove 48 surrounding the protrusion), the entire insert 36, portions 62 or 64 of the insert 60, separate outsole components, or any combination thereof, may comprise the thermoplastic copolyester elastomer foam as described herein. The sole component and the insert may be manufactured by foaming the thermoplastic copolyester elastomer as described herein, for example by injection molding or by injection molding followed by compression molding as described herein. In some aspects, the thermoplastic copolyester elastomer foam may be formed by physical foaming of the composition. Thermoplastic copolyester elastomer foams and components can exhibit improved physical properties, including enhanced energy return and enhanced split tearing, reduced density, or one or more combinations thereof.

[0085] The sole component 14, typically positioned between the wearer's foot and the ground, provides attenuation of ground reaction forces (i.e., cushioning), adhesive friction, and can control foot movements such as pronation. Like conventional footwear, the sole component 14 may include an insole (not shown) located within the upper 12. In some aspects, the sole component is an insole or sockliner, or a multi-part assembly including an insole or sockliner, and may also include an insole or sockliner located within the upper, wherein the insole or sockliner is wholly or partially formed of the thermoplastic copolyester elastomer foam described herein. Footwear articles described herein may include insoles or sockliners wholly or partially formed of the thermoplastic copolyester elastomer foam described herein.

[0086] like Figure 2 As can be seen, the sole component 14 consists of a first portion 26 having an upper surface 27 with recesses 28 formed therein. The upper surface 27 is secured to the upper 12 using adhesive or other suitable fastening means. More than one generally horizontal rib 30 is formed on the exterior of the first portion 26. In some aspects, the rib 30 extends rearward along the first portion 26 from the center portion of the forefoot portion 20 on the inner side 16, around the heel portion 24, and forward on the outer side 18 of the first portion 26 to the center portion of the forefoot portion 20.

[0087] Part 26 provides an external attachment friction surface for the sole component 14. In some aspects, it should be understood that a separate outsole component can be attached to the lower surface of part 26. When a separate outsole component is attached to the lower surface of part 26, part 26 is a sole interlayer component. In some aspects, the article is a sole interlayer component for footwear articles. In other aspects, the article is a sole interlayer-outsole component for a combination of footwear articles.

[0088] In some respects, the item is an insert. Insert 36 can be received in recess 28. For example... Figure 2 As illustrated, insert 36 can provide cushioning or elasticity in the sole component. First portion 26 can provide structure and support for insert 36. In such an aspect, first portion 26 can be formed of a material with a higher density and / or stiffness compared to insert 36, such as non-foamed materials including, for example, rubber and thermoplastic polyurethane, as well as foamed materials. In some aspects, insert 36 can be formed of thermoplastic copolyester elastomer foam as disclosed herein.

[0089] The insert 36 has a curved rear surface 38 to mate with the curved rear surface 32 of the recess 28, and a transverse front surface 40 to mate with the transverse front surface 34 of the recess 28. The upper surface 42 of the insert 36 contacts the upper 12 and is secured to the upper 12 by adhesive or other suitable fastening means. For example, when the insert 36 is present, the recess 28 can extend from the heel portion 24 to the forefoot portion 20. In some aspects, the rear surface 32 of the recess 28 is curved to generally follow the contour of the rear of the heel portion 24, and the front surface 34 of the recess 28 extends transversely across the first portion 26.

[0090] like Figure 3 As best viewed from the center, the lower surface 44 of the mating surface of the first portion 26 includes more than one protrusion 46. Each protrusion 46 is surrounded by a groove 48. More than one transverse slot 50 is formed in the lower surface 44, extending between adjacent protrusions 46. A longitudinal slot 52 extends along the lower surface 44 from the heel portion 24 to the forefoot portion 20.

[0091] Figure 4 and Figure 5 The bottom and top views of insert 60 are shown, which can be used in a shoe sole component as described herein. Insert 60 is similar to insert 36, but as... Figure 4 and Figure 5 As illustrated in the figure, the insert 60 is formed of two types of materials 62 and 64, wherein at least one of the materials is a thermoplastic copolyester elastomer foam as disclosed herein. Figure 4 A bottom view of the insert 60 is shown, while Figure 5A top view of an insert 60 is shown, which is formed of two types of materials 62 and 64, wherein the insert is placed inside a first portion 66 to form a sole component 14. Inserts having more than two types of materials can also be used, at least one of which is a thermoplastic copolyester elastomer foam as disclosed herein. Figure 4 and Figure 5 In the example illustrated, a portion of the first material 62 can be used for the heel area of ​​the insert, and a portion of the second material 64 can be used for the toe area of ​​the insert. A higher-density material can be used to support the heel area, while a lower-density material can be used to support the toe area. For example, the density of the first material can be at least 0.02 g / cm³ greater than the density of the second material. The shapes of the portions of the two materials 62 and 64 of the insert can be any suitable shape. For example, the heel area can be wedge-shaped. Inserts formed from these two types of materials can be useful in running shoes as well as in basketball shoes.

[0092] In some respects, an item can be a component other than the sole component. For example, an item can be an upper or an upper component. An upper component refers to a component that is stitched or otherwise joined to one or more other components to form the upper. The material of the upper typically contributes to properties such as breathability, conformability, weight, and softness or suppleness. A substructure component refers to a component that is joined to one or more other components to form the lower part of a footwear item. The substructure can include, for example, an outsole and a midsole. The choice of outsole material and design contributes to factors such as durability, traction, and pressure distribution during use. The midsole material and design contribute to factors such as cushioning and support. Grindery components include all additional components that can be attached to the upper, substructure, or both. Polished components may include, for example, eyelets, toe puffs, shanks, nails, laces, velcro, buckles, backers, linings, padding, heel backing, heel foxing, and toe caps.

[0093] In some respects, the upper is a lasted upper. As used herein, "lasted upper" refers to an upper formed into the shape of a shoe before being attached to the sole by one or more mechanical means. A lasted upper may include a heel counter formed to shape the heel portion of the upper. A lasted upper may include a strobe or strobe plate typically attached to the upper via a strobe stitch.

[0094] The method for producing the disclosed foam.

[0095] In some instances, the disclosed foamed polymer materials can be prepared by a variety of methods as disclosed herein and as known in the art. That is, the disclosed articles or articles such as sole interlayers, sole interlayer components, inserts, and insert components can be prepared by injection molding the melt compositions described herein using physical foaming agents and / or chemical foaming agents.

[0096] This document discloses a method for manufacturing foam articles, the method comprising: forming a mixture of a molten polymer material and a foaming agent, wherein the polymer material comprises the disclosed thermoplastic copolyester elastomer; injecting the mixture into a mold cavity; foaming the molten polymer material to form a foamed molten polymer material; solidifying the foamed molten polymer material to form a foam article having a microporous foam structure; and removing the foam article from the mold cavity.

[0097] A method for manufacturing foam articles is also disclosed, the method comprising: forming a mixture of a molten polymer material and a foaming agent, wherein the polymer material comprises the disclosed thermoplastic copolyester elastomer; injecting the mixture into a mold cavity; foaming the molten polymer material to form a foamed molten polymer material; solidifying the foamed molten polymer material to form a foam article having a microporous foam structure; and removing the foam article from the mold cavity; wherein the mixture has an injection temperature; and wherein the injection temperature is from approximately the melting temperature of the thermoplastic copolyester elastomer to approximately 50°C above the tail temperature of the thermoplastic copolyester elastomer.

[0098] A method for manufacturing foam articles is also disclosed, the method comprising: forming a mixture of a molten polymer material and a foaming agent, wherein the polymer material comprises the disclosed thermoplastic copolyester elastomer; injecting the mixture into a mold cavity; foaming the molten polymer material to form a foamed molten polymer material; solidifying the foamed molten polymer material to form a foam article having a microporous foam structure; and removing the foam article from the mold cavity; wherein the foaming occurs at a foaming temperature; and wherein the foaming temperature is from approximately the melting temperature of the thermoplastic copolyester elastomer to approximately 50°C above the tail temperature of the thermoplastic copolyester elastomer.

[0099] Dynamic scanning calorimetry (DSC) is used to determine the melting and tail temperatures of thermoplastic copolyester elastomers, and exemplary methods are described in the examples below. Briefly, 10-30 mg of undried resin pellets are cycled from -90°C to 225°C at 20°C / min and cooled to -90°C at 10°C / min. In some cases, experiments are run using a heat-cold-heat curve at a ramp rate of 10°C / min, with a minimum temperature of 0°C and a maximum temperature of 250°C. Analysis should be performed in duplicate. T is recorded from the second cycle. m Value and T g The melt "peak" is determined as the local maximum value of the second heating cycle. If more than one peak exists in the DSC curve, the peak occurring at the hotter temperature is selected as the temperature reference. The tail is determined as the intersection of the tangent to the line on the higher temperature side of the melt peak and the extrapolated baseline. A schematic diagram of the method used to determine the peak temperature and tail temperature is illustrated in [the diagram]. Figure 7 As shown in the image.

[0100] For example, the disclosed foamed polymer material can be prepared using a suitable extruder. The extruder (e.g., a single-screw or twin-screw extruder) can be used to provide the composition. The extruder may have a motor to rotate the screw inside the extruder. The extruder can be a single-screw or twin-screw extruder made of various elements of different sizes and pitches suitable for mixing or kneading the specific material used. In some instances, the extruder has a twin-screw design.

[0101] Multiple components constituting the compositions used to form the various examples of thermoplastic copolyester elastomer foams described herein are added to an extruder through one or more ports. The components may be added as a melt or as appropriately sized solid particles, such as fragments or spheres, which are melted in stages as they are mixed in the extruder barrel. The contents of the extruder may be heated to melt the composition. A supercritical fluid may be added to the melt as a physical blowing agent. In certain examples, the thermoplastic copolyester elastomer foam is prepared using a physical blowing agent that foams the composition after it leaves the extruder, and thus the thermoplastic copolyester elastomer foam is substantially free of chemical blowing agents or their decomposition products.

[0102] In some instances, the composition can be added as a melt at temperatures close to or at which the ionic crosslinking between polymer chains dissociates. At lower temperatures, the ionic moieties can reform or reassociate. Due to ionic crosslinking, the degree of crosslinking of the composition during processing can be controlled by temperature control; by inducing a temperature drop at a desired point to increase crosslinking, this results in an increase in the modulus or viscosity of the molten resin as the ionic moieties reassociate.

[0103] If a chemical blowing agent is used, the processing (melting) temperature used can be sufficiently lower than the temperature at which the blowing agent will be triggered. To foam the composition, the temperature near the extruder exit can be raised to near or at the trigger temperature of the chemical blowing agent, thereby producing a chemically foamed thermoplastic copolyester elastomer foam as the composition leaves the extruder (e.g., as the composition is injected into an injection mold).

[0104] Alternatively or additionally, a physical foaming agent can be used to foam the composition to form a physically foamed thermoplastic copolyester elastomer foam, or a physically and chemically foamed thermoplastic copolyester elastomer foam. For example, supercritical fluids such as supercritical carbon dioxide or supercritical nitrogen can be mixed with the molten polymer composition in the barrel of an extruder. As the mixture of the molten composition containing one or more thermoplastic copolyester elastomers and the supercritical fluid exits the extruder, the pressure drop between the higher pressure inside the extruder and the lower pressure outside the extruder causes the supercritical fluid to transition into the gas phase and foams the molten polymer composition.

[0105] Various examples include methods of manufacturing footwear articles or components for footwear articles. In some examples, methods of manufacturing footwear articles include injection molding compositions to form the thermoplastic copolyester elastomer foam described herein to produce foam articles or components of articles such as footwear articles. The article or component of the article may be a sole interlayer or a component of a sole interlayer, and the method may include providing an upper and an outsole for the footwear article; and combining the sole interlayer or sole interlayer component, the upper, and the outsole to manufacture the footwear article. In some examples, methods of manufacturing footwear articles include combining an article comprising a thermoplastic copolyester elastomer foam, an upper, and an outsole to manufacture the footwear article.

[0106] Articles or parts thereof, such as shoe sole interlayers, shoe sole interlayer components, inserts, and insert components, can be prepared by injection molding the melt compositions described herein using a physical foaming agent. Injection molding can be performed using a screw-type syringe, which allows for maintaining and controlling the pressure within the syringe barrel. An injection molding machine can allow for the metering and delivery of supercritical fluids, such as carbon dioxide or nitrogen, into the composition prior to injection. The supercritical fluid can be mixed into the composition within the syringe barrel and then injected into a mold. The supercritical fluid can then expand to create cell nuclei to form a physical foam within the mold. Injection molding can include physically foaming the compositions described herein using microporous foam injection molding processes such as, for example, the MuCell process (Trexcel Inc., Royal Oak, Michigan, USA).

[0107] In some instances, the thermoplastic copolyester elastomer foams of various examples described herein are manufactured using a process involving impregnating a polymer composition with a physical blowing agent at a first concentration or a first pressure (e.g., at or above the softening temperature of the composition). As used herein, the term "impregnation" generally means dissolving or suspending a physical blowing agent in the composition. The impregnated composition can then be foamed, or can be cooled (where applicable) and re-softened (where applicable) for blowing at a later time.

[0108] In some cases, the impregnated composition is foamed by reducing the solubility of the physical blowing agent in the polymer matrix via pressure or temperature changes. The reduction in the solubility of the physical blowing agent can release additional amounts of the impregnated physical blowing agent from the composition (e.g., for secondary expansion to create initially formed micropores in the composition) to further blow the composition to form a foam composition (e.g., a foam composition having a microporous structure).

[0109] In addition to injection molding, the thermoplastic copolyester elastomer foams of this disclosure can be foamed and molded using a variety of processes known in the art. For example, the thermoplastic copolyester elastomer foams can be formed into various shapes and sizes, such as sheet foams, filament foams or strand foams, and granular (e.g., bead) foams. These various forms of foam can then be used in different ways. For example, like injection-molded foams, sheet foams and filament or strand foams can be used directly as finished foam articles, or they can be shaped (e.g., cut, polished, or trimmed) to form finished foam articles, or they can be compression molded to form finished foam articles. Optionally, the thermoplastic copolyester elastomer foams can undergo an annealing process as part of forming finished foam articles. The microspheres of the composition can be used to form individual granular thermoplastic copolyester elastomer foams, or they can be foamed and molded to form monolithically molded foam articles comprising individual portions of foam attached to each other.

[0110] The thermoplastic copolyester elastomer foams of various examples described herein can be further shaped or molded using any known method for forming articles from thermoplastic materials. Optionally, thermoplastic copolyester elastomer foams of this disclosure that have been foamed using any suitable blowing process (e.g., blowing with physical and / or chemical blowing agents), including those foamed by injection molding using only physical blowing agents, can then be compression molded to form compression molded foams.

[0111] In some instances, the thermoplastic copolyester elastomer foam of this disclosure can be prepared by a process comprising: (i) softening the composition (e.g., by heating at or above the softening temperature of the composition); (ii) simultaneously with or sequentially (where applicable) contacting the composition with a physical blowing agent at a first concentration or a first pressure sufficient to drive a certain amount of physical blowing agent into the composition or to combine the physical blowing agent with the composition; (iii) changing the concentration or pressure of the physical blowing agent (e.g., reducing the pressure or concentration) to a second concentration or a second pressure that effectively foams the composition, thereby forming a thermoplastic copolyester elastomer foam (e.g., a thermoplastic copolyester elastomer foam having a microporous structure); and (iv) after the change, cooling (where applicable) the thermoplastic copolyester elastomer foam (e.g., cooling to a temperature below the softening temperature of the composition) to form a cured thermoplastic copolyester elastomer foam.

[0112] In other instances, the thermoplastic copolyester elastomer foam of this disclosure is prepared by: (i) in some instances, contacting (e.g., dissolving or suspending) the composition with a first concentration of a chemical blowing agent at or above the softening temperature of the composition; (ii) triggering the chemical blowing agent to foam the composition, thereby forming a thermoplastic copolyester elastomer foam (e.g., a thermoplastic copolyester elastomer foam with a microporous structure); and (iii) after triggering, in some instances, cooling the thermoplastic copolyester elastomer foam to a temperature, for example, below its softening temperature, to form a cured thermoplastic copolyester elastomer foam. In some instances, the “triggering” of the chemical blowing agent is carried out by any suitable method, including heating the composition containing a certain concentration of the chemical blowing agent to a temperature sufficient to “trigger” the chemical blowing agent, wherein the concentration of the chemical blowing agent effectively foams the composition, thereby forming a thermoplastic copolyester elastomer foam (e.g., a thermoplastic copolyester elastomer foam with a microporous structure). In some instances, contact includes pressure contact ranging from about 10 MPa to about 100 MPa (e.g., from about 30 MPa to about 100 MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 60 MPa, or about 40 MPa to about 70 MPa).

[0113] Chemical blowing agents can be endothermic or exothermic, referring to the type of decomposition they undergo to produce gases used for foaming. Decomposition may be a result of thermal energy in the system. Endothermic blowing agents absorb energy and typically release gases, such as carbon dioxide, upon decomposition. Exothermic blowing agents release energy and produce gases, such as nitrogen, upon decomposition. Regardless of the chemical blowing agent used, the thermal variables of the molded polymer composition and the thermal variables of the blowing agent to be decomposed are linked, such that process parameters are selected to allow the polymer to be molded and the blowing agent to decompose at an appropriate stage of the molding operation.

[0114] In another instance, the disclosed foamed polymer materials and articles can be prepared using a system such as that disclosed in U.S. Patent Application No. 62 / 734,912, which is incorporated herein by reference. In summary, the system provides reduced pressure loss throughout the system, and control (e.g., intentionally increasing or decreasing) the elongation, apparent shear, and / or zero-shear viscosity of the molten polymer material flowing into the mold. The method includes flowing molten polymer material from an upstream device into a shot tuning chamber and adjusting the temperature, pressure, or both within the shot tuning chamber to produce a tuned molten polymer material. The method further includes flowing the tuned molten polymer material from the shot tuning chamber into a mold cavity. It will be understood that fine-tuning the temperature of the molten polymer material and / or the pressure applied to the molten polymer material allows the system to have a desired effect on the physical and mechanical properties of the molded article. In particular, the temperature of the molten polymer material can be controlled to achieve a desired range of shear / stretch viscosity, which reduces (e.g., substantially eliminates) uncontrolled bubble growth and / or nucleation. In one example, the method may further include adjusting (e.g., increasing and / or decreasing) the pressure in the mold cavity via a gas back pressure (GCP) component before or simultaneously with the molten polymer material flowing from the injection tuning chamber into the mold cavity. In such an example, the molten polymer material may flow into the mold cavity at a pressure significantly higher than ambient pressure. Furthermore, the GCP may be introduced into the mold cavity to control nucleation and bubble growth during polymer foaming and to increase the surface quality of the molded article. Control of nucleation and bubble growth enhances the pore density uniformity and mechanical properties of the molded polymer material. In some examples, improved pore density uniformity can be particularly beneficial in articles with low density, such as those with a density of less than or equal to 0.3 g / cm³, and / or in articles with large dimensions, such as those with a thickness of ≥1.0 cm.

[0115] In several aspects, the system may include an injection tuning chamber configured to receive molten polymer material from an upstream device. The injection tuning chamber is also configured to regulate one or more of the temperature and pressure applied to the molten polymer material to produce and dispense the regulated molten polymer material. In this way, the system can selectively regulate the temperature and / or pressure of the tuning chamber to achieve desired properties, as previously mentioned. In one example, the system may also include an adjustable mold runner configured to regulate fluid communication between the injection tuning chamber and a mold cavity in the mold. In another example, the system may also include a GCP assembly coupled to the mold cavity and configured to regulate the amount of back pressure gas flowing into and out of the mold cavity. Providing GCP regulation while the polymer material enters the mold and cools within it allows for further tuning of the polymer material.

[0116] Alternatively, the disclosed foamed polymer materials and articles can be prepared using the methods and systems described in International Patent Application No. PCT / US2018 / 035128. In short, the method may include a method for molding a single-phase solution comprising a polymer composition and a gas. The polymer composition and gas are held under pressure during the molding operation to prevent dissolved gas in the polymer composition from escaping from the solution and forming a porous structure. The single-phase solution is introduced into a mold cavity for molding purposes and pressurized to a mold pressure sufficient to maintain the single-phase solution as a single-phase solution when the mold cavity is filled. After the mold cavity is filled with the single-phase solution under pressure, the resulting article may solidify, embedding the compressed gas, or the article may be exposed to a pressure reduction, causing the embedded gas to form a microporous structure.

[0117] The method may include forming a single-phase solution, such as by introducing pressurized gas into the barrel (e.g., screw) of an injection molding apparatus along with a polymer composition, which, for example, is derived from about T as described elsewhere. m Up to T higher than that of thermoplastic copolyester elastomers 尾部The gas melts at approximately 50°C, and the cylinder of the injection molding apparatus effectively mixes and dissolves the gas with the polymer composition under pressure. The method continues by pressurizing the mold cavity to above atmospheric pressure, reaching the mold pressure. Atmospheric pressure is the pressure of the environment in which the mold cavity is exposed (e.g., general ambient pressure). The mold pressure is at least the pressure required to maintain the single-phase solution as a single phase. The method also includes injecting the single-phase solution into the pressurized mold cavity. The method further includes maintaining the mold pressure within the mold cavity at least during the injection of the single-phase solution. As a result, the pressure within the mold cavity prevents gas from escaping from the solution to form a two-phase mixture (e.g., foaming) upon exiting the injection molding apparatus. When the pressure is maintained, premature foaming of the polymer composition is avoided upon injection from the injection molding apparatus, allowing for decoupling of process parameters associated with the foaming agent and the polymer composition.

[0118] In another example, the disclosed foamed polymer material can be prepared using a molding system comprising means configured to receive and heat the polymer material to form a molten polymer material. The molding system further includes an injection tuning chamber configured to receive the molten polymer material from the means and to regulate the temperature or pressure applied to the molten polymer material. The molding system also includes an adjustable die flow channel configured to regulate the flow of the molten polymer material between the injection tuning chamber and the die cavity. In one example, the means may be an injection unit or an extrusion unit. This molding system allows the properties of the polymer material to be adapted to achieve the desired end-use objectives.

[0119] In some aspects, this disclosure relates to compression-molded thermoplastic copolyester elastomer foams, and to methods for forming compression-molded thermoplastic copolyester elastomer foams for footwear or sports equipment articles and other applications. In some instances, the method may include a process comprising: providing (e.g., preparing) a thermoplastic copolyester elastomer foam preform, and then compression-molding the thermoplastic copolyester elastomer foam preform to form a compression-molded thermoplastic copolyester elastomer foam. For example, the thermoplastic copolyester elastomer foam can be compression-molded by placing the thermoplastic copolyester elastomer foam preform in a compression mold having a height less than the initial height of the thermoplastic copolyester elastomer foam preform and closing the mold, thereby compressing the thermoplastic copolyester elastomer foam preform to the height of the mold. Simultaneously with or sequentially with the compression, the thermoplastic copolyester elastomer foam preform may be heated within the closed compression mold. During compression molding, the temperature of at least a portion of the thermoplastic copolyester elastomer foam preform within the closed mold can be raised to a temperature within ±30°C of the softening temperature of the composition. The temperature can be raised by heating the closed mold. After raising the temperature, while the thermoplastic copolyester elastomer foam preform remains closed in the compression mold, the temperature of at least a portion of the thermoplastic copolyester elastomer foam preform can be lowered. The temperature can be lowered by cooling the closed mold. Lowering the temperature of at least a portion of the thermoplastic copolyester elastomer foam preform can reduce the temperature to a temperature at least 35°C below the softening temperature of the composition, thereby forming the compression-molded thermoplastic copolyester elastomer foam. After cooling, the compression mold can be opened, and the compression-molded thermoplastic copolyester elastomer foam can be removed from the compression mold.

[0120] Examples contemplated herein relate to methods of manufacturing footwear articles or sports equipment articles. For example, the method may include: providing components of a footwear article according to this disclosure, such as a sole interlayer and inserts, and combining said components with a footwear upper and outsole to form the footwear article.

[0121] A method of manufacturing compression-molded thermoplastic copolyester elastomer foam articles, such as shoe sole interlayers and inserts, or components of articles, such as components of shoe sole interlayers or inserts, as described herein, includes: forming a thermoplastic copolyester elastomer foam preform; and compressing the thermoplastic copolyester elastomer foam preform to manufacture a compression-molded thermoplastic copolyester elastomer foam. In some examples, the foam preforms of various examples described herein are obtained by blowing the composition in at least one dimension (e.g., a vertical dimension) with a foaming agent at approximately 150 percent to about 240 percent (e.g., from about 150 percent to about 220 percent; about 150 percent to about 200 percent, about 175 percent to about 225 percent, about 180 percent to about 230 percent, or about 160 percent to about 240 percent). In some instances, the blown composition can be compressed and molded to about 120 percent to about 200 percent in at least one dimension (e.g., from about 120 percent to about 180 percent; about 130 percent to about 190 percent; about 150 percent to about 200 percent; or about 160 percent to about 190 percent).

[0122] Therefore, for example, if the composition has a foaming percentage of about 200%, the blown composition can be compressed to about 180% to be compressed to a net 20%. In another example, if the composition is blown into a 20 mm (height) × 10 cm (width) × 5 cm (depth) sheet (wherein hereinafter, "mm" will be used to indicate millimeters and "cm" will be used to indicate centimeters), and the sheet is compressed to 20% in the height direction, the compressed-molded sheet will have dimensions of 18 mm (height) × 10 cm (width) × 5 cm (depth). In some instances, the compression molding is substantially maintained.

[0123] In some instances, thermoplastic copolyester elastomer foams are manufactured using a process involving impregnating a composition with a physical blowing agent at a first concentration or pressure (e.g., at or above the softening temperature of the composition). The impregnated composition can then be foamed, or cooled (where applicable) and re-softened (where applicable) for blowing at a later time. In some cases, the impregnated composition foams by reducing the temperature or pressure, affecting the solubility of the physical blowing agent. The reduction in the solubility of the physical blowing agent can release additional amounts of the impregnated physical blowing agent from the composition for further blowing of the composition to form a thermoplastic copolyester elastomer foam (e.g., a thermoplastic copolyester elastomer foam with a microporous structure).

[0124] In some instances, the compression molding process is performed by heating a thermoplastic copolyester elastomer foam preform within a closed compression mold. The thermoplastic copolyester elastomer foam preform is heated to a temperature close to its softening temperature to allow the foam to retain the shape of the compression mold. For example, the foam preform may be heated to a temperature within ±30°C, ±20°C, ±10°C, or ±5°C of its softening temperature. For instance, the thermoplastic copolyester elastomer foam preform may be heated to a temperature ranging from about 100°C to about 250°C, or from about 140°C to about 220°C, or from about 100°C to about 150°C, or from about 130°C to about 150°C.

[0125] The material used to form the compression mold can be any material that can withstand the temperatures used during the process, such as machined metals, including aluminum. The compression mold can be made using two parts, such as a top mold and a bottom mold. Depending on the shape of the foam part to be molded, multi-part molds can be used to facilitate the release of the compressed foam from the mold.

[0126] Injection-molded thermoplastic copolyester elastomer foams can have a closed skin. This closed skin can also be formed by compression molding a thermoplastic copolyester elastomer foam preform in a compression mold. However, during compression molding, care should be taken to avoid subjecting the thermoplastic copolyester elastomer foam preform to conditions that cause an excessive amount of closed-cell structure to collapse. One way to avoid collapsing an excessive amount of closed-cell structure is to control the temperature of the thermoplastic copolyester elastomer foam during the compression molding process, for example, by controlling the temperature of the mold. For example, during the compression molding step, the heating of the thermoplastic copolyester elastomer foam preform in the compression mold can be sustained for a period ranging from 100 seconds to 1,000 seconds or from 150 seconds to 700 seconds.

[0127] After the thermoplastic copolyester elastomer foam has been heated at an appropriate temperature in a compression mold for a desired duration to soften it to a desired level, the softened preform is cooled to a temperature, for example, at least 35°C, 50°C, or 80°C below its softening temperature, to re-solidify the softened foam, thereby forming a compression-molded foam. After cooling, the compression-molded thermoplastic copolyester elastomer foam is removed from the compression mold. The cooling of the foam preform in the compression mold after heating can be carried out for a period ranging from 50 seconds to 1,000 seconds, or from 100 seconds to 400 seconds.

[0128] In the thermoplastic copolyester elastomer foams of this disclosure, the composition comprising one or more thermoplastic copolyester elastomers has a foam structure with a density of about 0.7 g / cm³, 0.5 g / cm³, 0.4 g / cm³, 0.3 g / cm³, or less. The thermoplastic copolyester elastomer foam has a density of about 0.1 g / cm³ to about 0.22 g / cm³, about 0.2 g / cm³ to about 0.35 g / cm³, or about 0.1 g / cm³ to about 0.35 g / cm³. The thermoplastic copolyester elastomer foam can be foamed using any of the methods described above. The foams and components disclosed herein may have densities ranging from 0.02 g / cm³ to 0.22 g / cm³, or from 0.03 g / cm³ to 0.12 g / cm³, or from 0.04 g / cm³ to 0.10 g / cm³, or from 0.11 g / cm³ to 0.12 g / cm³, or from 0.10 g / cm³ to 0.12 g / cm³, or from 0.15 g / cm³ to 0.2 g / cm³, or from 0.15 g / cm³ to 0.30 g / cm³. Optionally or additionally, the foam preform may have a density from 0.01 g / cm³ to 0.10 g / cm³, or from 0.02 g / cm³ to 0.08 g / cm³, or from 0.03 g / cm³ to 0.06 g / cm³, 0.08 g / cm³ to 0.15 g / cm³, or from 0.10 g / cm³ to 0.12 g / cm³. For example, the density of compression-molded foam parts may be from 0.15 g / cm³ to 0.2 g / cm³, and the density of foam preforms may be from 0.10 g / cm³ to 0.12 g / cm³. Thermoplastic copolyester elastomer foam may be included in components of footwear articles as described above, for example, as... Figure 1 The shoe sole interlayer 146 is depicted in the image.

[0129] Foam properties.

[0130] While the thermoplastic copolyester elastomer foams described herein can be used to manufacture any of a variety of components, including those for footwear articles, in certain aspects, components include midsoles, outsoles, insoles, or inserts. Other articles may include tongue pads, collar pads, and combinations thereof. As described above and in more detail below, articles incorporating the thermoplastic copolyester elastomer foams described herein can exhibit a unique balance of beneficial physical properties such as high energy return, high tear resistance, low density, and low compression set. Furthermore, thermoplastic copolyester elastomer foams can be reprocessed (e.g., for recycling) with minimal loss of physical properties, providing a solution for material sustainability. Thermoplastic copolyester elastomer foams can be injection molded, or injection molded and subsequently compression molded.

[0131] In several aspects, the disclosed foamed polymer material can have a porous foam structure. In some cases, the porous foam structure can be a closed-cell foam structure. In other cases, the porous foam structure can be an open-cell foam structure. In some cases, the porous foam structure has an average pore size from about 50 micrometers to about 5 mm; from about 100 micrometers to about 1 mm; or from about 50 micrometers to about 1 mm.

[0132] In articles including the thermoplastic copolyester elastomer foam described herein, the thermoplastic copolyester elastomer foam portion of the article may exhibit beneficial split tearing, such as high split tearing in the sole component of footwear articles. In some aspects, the thermoplastic copolyester elastomer foam may have split tearing values ​​of about 1.0 kg / cm to 4.5 kg / cm, about 1.6 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 3.5 kg / cm, or about 2.5 kg / cm to 3.5 kg / cm. Split tearing can be measured according to ASTM D3574-95. In some aspects, the thermoplastic copolyester elastomer foam is injection molded (i.e., after being formed by injection molding and removed from the injection mold, it is not exposed to a separate compression molding step), or it is injection molded and subsequently compression molded in a separate compression mold having a different size than the mold used in the injection molding step. Thermoplastic copolyester elastomer foams can have split tear ratios of about 0.08 kg / cm to 4.0 kg / cm, about 0.9 kg / cm to 3.0 kg / cm, about 1.0 kg / cm to 2.0 kg / cm, about 1.0 kg / cm to 1.5 kg / cm, or about 2 kg / cm. In some aspects, the thermoplastic copolyester elastomer foam is injection molded and has split tear ratios of about 0.07 kg / cm to 2.0 kg / cm, or about 0.8 kg / cm to 1.5 kg / cm, or about 0.9 kg / cm to 1.2 kg / cm, or about 1.5 kg / cm to 2.2 kg / cm.

[0133] In some aspects, the thermoplastic copolyester elastomer foam portion of the article or article component may have a stiffness of about 30 N / mm to 275 N / mm, about 40 N / mm to 275 N / mm, about 40 N / mm to 100 N / mm, about 100 N / mm to 200 N / mm, about 50 N / mm to 150 N / mm, about 50 N / mm to 100 N / mm, or about 50 N / mm to 85 N / mm, as determined using a cyclic tensile testing system as described below. In some aspects, the thermoplastic copolyester elastomer foam of the article or article component is formed by injection molding or by injection molding and subsequent compression molding. Thermoplastic copolyester elastomer foams can have stiffnesses of about 30 N / mm to 275 N / mm, about 40 N / mm to 275 N / mm, about 40 N / mm to 100 N / mm, about 100 N / mm to 200 N / mm, about 50 N / mm to 150 N / mm, about 50 N / mm to 100 N / mm, or about 50 N / mm to 85 N / mm, as determined using a cyclic tensile testing system as described below.

[0134] Energy efficiency, a measure of the percentage of energy returned by the thermoplastic copolyester elastomer foam portion of an article or component when it is released after being compressed under load, can provide improved performance for athletic footwear, such as reducing energy loss or dissipation during running. This is especially true for running shoes and other athletic footwear. In some aspects, the thermoplastic copolyester elastomer foam portion of the articles and components provided herein has an energy return of approximately 50% to 95%, approximately 60% to 95%, approximately 60% to 90%, approximately 60% to 85%, approximately 65% ​​to 85%, or approximately 70% to 85%. In some aspects, the thermoplastic copolyester elastomer foam is injection molded, or injection molded and subsequently compression molded. The thermoplastic copolyester elastomer foam of this disclosure can have an energy return of about 50% to 95%, about 60% to 95%, about 60% to 95% (e.g., about 60% to 85%; about 65% to 80%; about 65% to 75%; about 70% to 80%; or about 75% to 80%; about 75% to 85%, about 75% to 90%, about 80% to 95%; or about 85% to 95%). The energy return can be measured as described in the embodiments below.

[0135] As discussed above, the thermoplastic copolyester elastomer foam portions of the articles and components provided herein exhibit low density, which advantageously reduces the weight of the midsole or other components containing thermoplastic copolyester elastomer foam. In some aspects, the thermoplastic copolyester elastomer foam, including the thermoplastic copolyester elastomer foam present in the midsole and midsole components, can have a density from about 0.02 g / cm³ to about 0.22 g / cm³; from about 0.03 g / cm³ to about 0.12 g / cm³; from about 0.04 g / cm³ to about 0.10 g / cm³; from about 0.11 g / cm³ to about 0.12 g / cm³; from about 0.10 g / cm³ to about 0.12 g / cm³; from about 0.15 g / cm³ to about 0.2 g / cm³. Density from about 0.15 g / cm³ to about 0.30 g / cm³; from about 0.05 g / cm³ to about 0.25 g / cm³; from about 0.05 g / cm³ to about 0.2 g / cm³; from about 0.05 g / cm³ to about 0.15 g / cm³; from about 0.08 g / cm³ to about 0.15 g / cm³; from about 0.08 g / cm³ to about 0.20 g / cm³; from about 0.08 g / cm³ to about 0.25 g / cm³; or from about 0.1 g / cm³ to about 0.15 g / cm³. In some respects, thermoplastic copolyester elastomer foams have densities of about 0.15 g / cm³ to about 0.3 g / cm³, from about 0.2 g / cm³ to about 0.35 g / cm³, or from about 0.15 g / cm³ to about 0.25 g / cm³.

[0136] The specific gravity of thermoplastic copolyester elastomer foam can be determined by testing at least three representative samples taken from the foam sample (e.g., 2-inch x 2-inch samples or 1-inch x 1-inch samples) or at least three whole foam articles or foam parts. Using a balance of appropriate accuracy, the samples are weighed, and after removing any air bubbles adhering to the surface of the weighed foam sample, the weight of each sample is determined in air and while the sample is fully immersed in distilled water at a temperature of 22°C ± 2°C. The specific gravity (SG) is then calculated by taking the weight of the sample in water and subtracting that weight from the weight of the sample in air, and then dividing that value by the weight of the sample in air, where all weights are in grams.

[0137] As discussed above, the thermoplastic copolyester elastomer foam of this disclosure exhibits a low density, which advantageously reduces the weight of the midsole or other components comprising the thermoplastic copolyester elastomer foam. Alternatively or additionally, the foam preform may have a density from 0.01 g / cm³ to 0.10 g / cm³, or from 0.02 g / cm³ to 0.08 g / cm³, or from 0.03 g / cm³ to 0.06 g / cm³, 0.08 g / cm³ to 0.15 g / cm³, or from 0.10 g / cm³ to 0.12 g / cm³. For example, the density of compression-molded foam components may be from 0.15 g / cm³ to 0.2 g / cm³, and the density of the foam preform may be from 0.10 g / cm³ to 0.12 g / cm³.

[0138] In some aspects, thermoplastic copolyester elastomer foams, including thermoplastic copolyester elastomer foams present in the midsole and midsole components, may have a specific gravity from about 0.05 to about 0.25; from about 0.05 to about 0.2; from about 0.05 to about 0.15; from about 0.08 to about 0.15; from about 0.08 to about 0.20; from about 0.08 to about 0.25; from about 0.1 to about 0.15; from about 0.02 to about 0.22; from about 0.03 to about 0.12; from about 0.04 to about 0.10; or from 0.11 to about 0.12; or from 0.10 to about 0.12; from about 0.15 to about 0.2; or from about 0.15 to about 0.30. Alternatively or additionally, the thermoplastic copolyester elastomer foam may have a specific gravity from about 0.01 to about 0.10; from about 0.02 to about 0.08; from about 0.03 to about 0.06; from about 0.08 to about 0.15; or from 0.10 to about 0.12. For example, the specific gravity of the thermoplastic copolyester elastomer foam may be from 0.15 to about 0.2, or from 0.10 to about 0.12. In some aspects, the thermoplastic copolyester elastomer foam has a specific gravity from about 0.15 to about 0.3; from about 0.2 to about 0.35, or from about 0.15 to about 0.25.

[0139] Several methods exist in the art for measuring the elasticity and / or energy return of foam. One method for measuring the elasticity of foam is based on ASTM D 2632-92, a test for solid rubber materials. For use with foam, the test sample is prepared as described in ASTM D2632-92, but a foam sample is used instead of a solid rubber sample. The test uses a plunger that is guided by a vertical rod and dropped from a height onto the test sample. The drop height is divided into 100 equal parts, and the height of the plunger's rebound is measured using this 100-part scale to determine the sample's elasticity. Alternative methods can also be used, which employ a ball of standard weight dropped onto the sample and measure the ball's rebound height to determine the sample's elasticity. In some aspects, elasticity and / or energy return are determined using force / displacement behavior measured using Instron Electropuls as described in the examples. For example, an Instron Electropuls E10000 with a stainless steel 45mm circular cross-section impact geometry can be used to evaluate compression of one or more different compression cycles. Compression cycles can include a running compression cycle consisting of a sample compressed from 0 Newtons (N) to 300 N and back to 0 N within 180 milliseconds (ms) under displacement control, followed by a 400 ms pause, totaling ~1.7 Hertz (Hz). A walking compression cycle consists of a sample compressed from 0 N to 144 N and back to 0 N within 600 ms, followed by a 400 ms pause, totaling ~1 Hz. The corresponding force-displacement data provide information on foam modulus (stiffness), hysteresis (energy efficiency), set, fatigue behavior, etc., after many cycles. Energy input can be considered as the integral of the force-displacement curve during the compressive force load. Hysteresis is considered as a ratio: (energy output) / (energy input), which can also be considered as the energy efficiency of the foam. Fatigue behavior is determined by the change in foam displacement at the maximum load of the cycle. Thousands of cycles of both running and walking compression cycles are performed, measuring all properties: stiffness, hysteresis, and fatigue.

[0140] In specific instances, the elasticity and / or energy return of the subsequently compressed thermoplastic copolyester elastomer foam can be from about 2000 mJ to about 3500 millijoules (mJ), or from about 2100 mJ to about 3400 mJ, or from about 2200 mJ to about 3300 mJ, or from about 2300 mJ to about 3200 mJ, or from about 2400 mJ to about 3100 mJ, or from about 2500 mJ to about 3100 mJ, or from about 2600 mJ to about 3100 mJ, or from about 2700 mJ to about 3100 mJ, or from about 2750 mJ to about 3100 mJ, or from about 2800 mJ to about 3100 mJ, or from about 2850 mJ to about 3100 mJ, or from about 2900 mJ to about 3100 mJ, or from about 2400 mJ to about 3050 mJ. 0 mJ, or from about 2500 mJ to about 3050 mJ, or from about 2600 mJ to about 3050 mJ, or from about 2700 mJ to about 3050 mJ, or from about 2750 mJ to about 3050 mJ, or from about 2800 mJ to about 3050 mJ, or from about 2850 mJ to about 3050 mJ, or from about 2900 mJ to about 3050 mJ, or from about 2400 mJ The range is approximately 3000 mJ to 2500 mJ, 2600 mJ to 3000 mJ, 2700 mJ to 3000 mJ, 2750 mJ to 3000 mJ, 2800 mJ to 3000 mJ, 2850 mJ to 3000 mJ, or 2900 mJ to 3000 mJ.

[0141] In specific instances, when the compression-molded thermoplastic copolyester elastomer foam has an elasticity and / or energy return greater than 45%, or greater than 50%, or greater than 55%, or greater than 60%, or greater than 65%, and the compression-molded thermoplastic copolyester elastomer foam can have an elasticity and / or energy return of from 0.02 g / cm³ to 0.15 g / cm³, or from 0.03 g / cm³ to 0.12 g / cm³, or from 0.04 g / cm³ to 0.10 g / cm³, or from 0.11 g / cm³... When the specific gravity is from 0.12 g / cm³ to 0.15 g / cm³ to 0.2 g / cm³, or from 0.15 g / cm³ to 0.30 g / cm³, the elastic and / or energy return of the subsequently compression-molded thermoplastic copolyester elastomer foam may be at least 6 percentage points, or at least 7 percentage points, or at least 8 percentage points, or at least 9 percentage points, or at least 10 percentage points, or at least 12 percentage points greater than that of the subsequently injection-molded thermoplastic copolyester elastomer foam that is not compression-molded.

[0142] Compression deformation is another important physical property of foams used as components in footwear or sports equipment. According to this disclosure, thermoplastic copolyester elastomer foams can have compression deformation ranging from 40% to 100%. For example, compression deformation can be from 45% to 90%, or from 40% to 80%, or from 50% to 75%.

[0143] Compression deformation can be measured by preparing samples of foam with a standard thickness (e.g., 10 mm). Parts with a thickness less than the standard can be stacked to create samples with a standard thickness. The samples are loaded into a metal compression plate and compressed to a height of 50 percent of the original thickness (e.g., 5 mm). The samples are placed in a 50°C oven on their sides for 6 hours. At the end of 6 hours, the samples are removed from the oven and from the metal compression plate and allowed to cool for 30 minutes. After cooling, the thickness of the samples is measured. The percentage of compression deformation (CS) is calculated by: (a) subtracting the final sample thickness from the original sample thickness, and (b) subtracting 50 percent of the compressed thickness from the original sample thickness, (c) dividing (a) by (b), and (d) multiplying the result by 100 to obtain the percentage of compression deformation (where all thicknesses are measured in millimeters).

[0144] The tear strength of foam can be measured using ASTM D3574-95. Although this method is for bonded and molded urethane foams, it can be used for thermoplastic copolyester elastomer foams according to this disclosure. The thermoplastic copolyester elastomer foam sample has a thickness of 10 mm ± 1 mm. If the thermoplastic copolyester elastomer foam has an outer layer, this outer layer should not be present on the test sample. A 3 cm long cut is placed at the center of one end of the sample, and five consecutive 2 cm sections are marked along the edge of the sample. The sample is tested as described in ASTM D3574-95. The tear strength of thermoplastic copolyester elastomer foam can range from 4 kg / cm to 10 kg / cm.

[0145] Tensile strength is another important physical property of foam. Thermoplastic copolyester elastomer foams can have tensile strengths ranging from 5 kg / cm² to 25 kg / cm², or from 10 kg / cm² to 23 kg / cm², or from 15 kg / cm² to 22 kg / cm². Tensile strength can be measured on punched specimens of foam in a standard-sized dumbbell shape, such as a width of 2.5 cm, a length of 11.5 cm, and a minimum thickness of 3 mm to 4 mm. The dumbbells follow the shape described in ASTM D412, Die C. The specimen is symmetrically loaded into a long-travel extensometer such as the Instron 2603-080 and tested using this long-travel extensometer, which allows for a minimum of 1000 percent strain, with a gauge length of 25 mm and a resolution of at least 0.1 mm. The tensile value at the failure point of the specimen (the point where the load initially falls during the test) is recorded.

[0146] Another physical property to consider when determining whether a foam is suitable for its intended use, such as in footwear or sporting goods, is its elongation at 300 percent. Thermoplastic copolyester elastomer foams can have an elongation of at least 125 kg / cm² or at least 150 kg / cm².

[0147] Thermoplastic copolyester elastomer.

[0148] The compositions provided herein may comprise one or more thermoplastic copolyester elastomers. The thermoplastic copolyester elastomers may comprise chain units derived from one or more olefins and chain units derived from one or more olefinic unsaturated acid groups. The composition may also comprise more than one cation in the anionic form of the acid groups in the ionically crosslinked thermoplastic copolyester elastomer. In some aspects, the composition is essentially only a thermoplastic copolyester elastomer and a metal cation. The thermoplastic copolyester elastomer may have a melt flow index of about 30 or less, about 20 or less, about 15 or less, about 10 or less, or about 5 or less.

[0149] Various thermoplastic copolyester elastomers can be processed into foam structures as described herein. In some aspects, the thermoplastic copolyester elastomer is a terpolymer of ethylene, acrylic acid, and methyl acrylate or butyl acrylate. In some aspects, the ratio III of the total weight parts of acrylic acid in the thermoplastic copolyester elastomer to the total weight of the thermoplastic copolyester elastomer is about 0.05 to about 0.6, about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.15 to about 0.5, or about 0.2 to about 0.5.

[0150] The compositions provided herein may comprise a thermoplastic copolyester elastomer comprising: (a) more than one first segment, each first segment derived from a dihydroxy-terminated polydiol; (b) more than one second segment, each second segment derived from a diol; and (c) more than one third segment, each third segment derived from an aromatic dicarboxylic acid. In several aspects, the thermoplastic copolyester elastomer is a block copolymer. In some aspects, the thermoplastic copolyester elastomer is a segment copolymer. In other aspects, the thermoplastic copolyester elastomer is a random copolymer. In still other aspects, the thermoplastic copolyester elastomer is a condensation copolymer.

[0151] In another aspect, the thermoplastic copolyester elastomer may have a weight-average molecular weight of about 50,000 Daltons to about 1,000,000 Daltons, about 50,000 Daltons to about 500,000 Daltons, about 75,000 Daltons to about 300,000 Daltons, about 100,000 Daltons to about 200,000 Daltons; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weight covering any of the foregoing ranges.

[0152] In another aspect, the thermoplastic copolyester elastomer may have a first segment to third segment ratio based on the weight of each of the first and third segments, ranging from about 1:1 to about 1:5, from about 1:1 to about 1:3, from about 1:1 to about 1:2, or from about 1:1 to about 1:3; or have one or more values ​​of the first segment to third segment ratio within any of the foregoing ranges, or have a range of first segment to third segment ratios covering subranges of any of the foregoing ranges.

[0153] In another aspect, the thermoplastic copolyester elastomer may have a second segment to third segment ratio from about 1:1 to about 1:2 based on the weight of each of the second and third segments, or from about 1:1 to about 1:1.52 based on the weight of each of the second and third segments; or have one or more values ​​of the second segment to third segment ratio within any of the foregoing ranges, or have a range of the second segment to third segment ratio covering any of the foregoing ranges.

[0154] In another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxy)diol having a weight-average molecular weight of about 250 Daltons to about 6,000 Daltons, about 400 Daltons to about 6,000 Daltons, about 350 Daltons to about 5,000 Daltons, or about 500 Daltons to about 3,000 Daltons; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weight covering any of the foregoing ranges.

[0155] In another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxide) glycol, such as poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; poly(hexamethylene ether) glycol; poly(heptamethylene ether) glycol; poly(octamethylene ether) glycol; poly(nonamethylene ether) glycol; poly(decamethylene ether) glycol; or mixtures thereof. In yet another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxide) glycol, such as poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; poly(hexamethylene ether) glycol. In another aspect, thermoplastic copolyester elastomers may have a first segment derived from poly(tetramethylene ether) glycol.

[0156] In another aspect, the thermoplastic copolyester elastomer may have a second segment derived from a diol having a molecular weight of less than about 250. The diol from which the second segment is derived may be a C2-C8 diol. In yet another aspect, the second segment may be derived from ethylene glycol; propylene glycol; butanediol; pentanediol; 2-methylpropanediol; 2,2-dimethylpropanediol; hexanediol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof. In yet another aspect, the second segment may be derived from 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof. In even another aspect, the second segment may be derived from 1,2-ethylene glycol. In yet another aspect, the second segment may be derived from 1,4-butanediol.

[0157] In another aspect, the thermoplastic copolyester elastomer may have a third segment derived from an aromatic C5-C16 dicarboxylic acid. The aromatic C5-C16 dicarboxylic acid may have a molecular weight of less than about 300 Daltons, about 120 Daltons to about 200 Daltons; or one or more values ​​of molecular weight within any of the foregoing ranges or a molecular weight range covering any of the foregoing ranges. In some cases, the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid, or a derivative thereof. In yet another aspect, the aromatic C5-C16 dicarboxylic acid is a diester derivative of terephthalic acid, phthalic acid, or isophthalic acid. In yet another aspect, the aromatic C5-C16 dicarboxylic acid is a dimethyl ester derivative of terephthalic acid or a dimethyl ester derivative thereof.

[0158] In another aspect, the thermoplastic copolyester elastomer comprises: (a) more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0159]

[0160] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and (b) more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0161]

[0162] R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0163] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit having a structure represented by Equation 3:

[0164]

[0165] Wherein R is H or methyl; where y is an integer having a value from 1 to 10; where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; an integer having a value from 5 to 50; an integer having a value from 5 to 40; an integer having a value from 4 to 30; an integer having a value from 4 to 20; an integer having a value from 2 to 10; or z can be any set or range of the foregoing integer values. In some aspects, R is hydrogen. In yet another aspect, R is methyl. In some cases, R is hydrogen, and y is an integer having a value of 1, 2, or 3. Alternatively, in other cases, R is a methyl group and y is an integer with a value of 1.

[0166] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit having a structure represented by Equation 4:

[0167]

[0168] Where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; an integer having a value from 5 to 50; an integer having a value from 5 to 40; an integer having a value from 4 to 30; an integer having a value from 4 to 20; an integer having a value from 2 to 10; or z can be any integer value or set of integer values ​​within the foregoing range or values, or any range of integer values ​​covering a subrange of the foregoing range of integer values.

[0169] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit having a weight-average molecular weight from about 400 Daltons to about 6,000 Daltons; about 400 Daltons to about 5,000 Daltons; about 400 Daltons to about 4,000 Daltons; about 400 Daltons to about 3,000 Daltons; about 500 Daltons to about 6,000 Daltons; about 500 Daltons to about 5,000 Daltons; about 500 Daltons to about 4,000 Daltons; about 500 Daltons to about 3,000 Daltons; about 600 Daltons to about 6,000 Daltons; about 600 Daltons to about 5,000 Daltons; about 600 Daltons to about 4,000 Daltons; about 600 Daltons to about 3,000 Daltons; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges, or a weight-average molecular weight range covering any of the foregoing ranges.

[0170] In another aspect, the thermoplastic copolyester elastomer comprises more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0171]

[0172] Where x is an integer having a value from 1 to 20; wherein the foam article has a microporous foam structure. In some aspects, in the foregoing formula, x is an integer having a value from 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2 to 14; 2 to 13; 2 to 12; 2 to 11; 2 to 10; 2 to 9; 2 to 8; 2 to 7; 2 to 6; 2 to 5; 2 to 4; or x can be any integer value or set of integer values ​​within the foregoing range or values, or any range of integer values ​​covering a subrange of the foregoing range of integer values. In other aspects, x is an integer having a value of 2, 3, or 4.

[0173] In another aspect, the thermoplastic copolyester elastomer comprises more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 6:

[0174]

[0175] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit within a weight percentage range based on the total weight of the thermoplastic copolyester elastomer, such that the weight percentage range is about 30 weight percent to about 80 weight percent; about 40 weight percent to about 80 weight percent; about 50 weight percent to about 80 weight percent; about 30 weight percent to about 70 weight percent; about 40 weight percent to about 70 weight percent; about 50 weight percent to about 70 weight percent; about 40 weight percent to about 65 weight percent; about 45 weight percent to about 65 weight percent; about 50 weight percent to about 65 weight percent; about 55 weight percent to about 65 weight percent; about 40 weight percent to about 60 weight percent; about 45 weight percent to about 60 weight percent; about 50 weight percent to about 60 weight percent; about 55 weight percent to about 60 weight percent; or any weight percentage value or set of weight percentage values ​​within any of the aforementioned weight percentage ranges, or any range of weight percentage values ​​covering any subset of the aforementioned ranges.

[0176] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have a maximum load of about 10 N to about 100 N; about 15 N to about 50 N; about 20 N to about 40 N; or any load value or set of load values ​​within any of the aforementioned load value ranges, or any range of load values ​​covering a subset of any of the aforementioned ranges.

[0177] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have an energy efficiency of more than or equal to about 50 percent; more than or equal to about 60 percent; more than or equal to about 70 percent; about 50 percent to 90 percent; about 60 percent to about 90 percent; about 70 percent to about 90 percent; or any energy efficiency value or set of energy efficiency values ​​within any of the foregoing energy efficiency ranges, or any range of energy efficiency values ​​covering any subset of the foregoing ranges.

[0178] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have an energy return of about 1 J to 15 J; about 2 J to 12 J; about 4 J to 10 J; or any energy return value or set of energy return values ​​within any of the aforementioned energy return ranges, or any range of energy return values ​​covering any subset of the aforementioned ranges.

[0179] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have a tensile modulus of about 1 MPa to 15 MPa; about 300 kPa to 3 MPa; about 500 kPa to about 2 MPa; and about 100 MPa to about 10 MPa; or any tensile modulus value or set of tensile modulus values ​​within any of the foregoing tensile modulus ranges, or any range of tensile modulus values ​​covering any subset of the foregoing ranges.

[0180] In another aspect, thermoplastic copolyester elastomers can possess zero-shear viscosity values, which can be determined as described below. In short, viscosity measurements can be collected using a flat parallel plate on a suitable rheometer, such as the TA Instruments DHR-3 rheometer. Typically, circular samples with a 25 mm cross-section and approximately 2 mm thickness are punched from a solid injection-molded substrate. The samples are dried before being placed in the rheometer. All samples are equilibrated at 180°C for 2–5 minutes and trimmed to obtain a final gap of <1 mm. Shear rates are performed from 0.01 s⁻¹. -1 up to 100s -1 Flow scanning experiments were conducted. Data were fitted to the Carreau, Carreau-Yasuda, and Williamson models, and the best fit was selected to record the zero-shear viscosity values. Polymer melt flow profiles were determined at temperatures, for example, 20°C above the melting point as described above by DSC. In several respects, the thermoplastic copolyester elastomer can have zero-shear viscosity values ​​of about 10 Pa·s to about 10,000 Pa·s; about 100 Pa·s to about 7,000 Pa·s; and about 1,000 Pa·s to about 5,000 Pa·s.

[0181] In some aspects, thermoplastic copolyester elastomers may include phase-separated domains. For example, more than one first segment derived from a dihydroxyl-terminated polydiol may be phase-separated into a domain primarily comprising the first segment. Furthermore, more than one second segment derived from the diol may be phase-separated into a domain primarily comprising the second segment. In other aspects, thermoplastic copolyester elastomers may include phase-separated domains primarily comprising more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxyl-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0182]

[0183] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000, and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and other phase-separated domains mainly comprising more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0184]

[0185] R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment. In other aspects, the thermoplastic copolyester elastomer may include phase-separated domains primarily comprising more than one first copolyester unit, each of the more than one first copolyester unit having a structure represented by Formula 4:

[0186]

[0187] Where z is an integer having a value from 2 to 60, and wherein the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons; and other phase-separated domains mainly comprising more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0188]

[0189] Where x is an integer with values ​​from 1 to 20.

[0190] Exemplary, but not limiting, thermoplastic polyester elastomers, including thermoplastic copolyester elastomers, that can be used in the disclosed methods, foams, and articles. 3078 4068 and 4556 (DuPont, Wilmington, Delaware, USA); Pelprene TM P30B, P40B and P40H (Toyobo USA Inc., New York, New York, USA); 5300 5400 and its blends (Samyang Corporation, Korea); Keyflex BT1028D, BT1033D, BT1035D, BT1040D, BT1045D and BT1047D (LG Chem, Korea); and KP3340, KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea).

[0191] In some aspects, the disclosed foamed polymer materials may also include one or more ionomers, such as Any of the polymers (DuPont, Wilmington, Delaware, USA). The thermoplastic copolyester elastomer foam described herein can be manufactured by a process / method comprising: receiving the composition described herein, and physically foaming the composition to form a thermoplastic copolyester elastomer foam having a density of about 0.7 g / cm³ or less, or 0.5 g / cm³ or less, or 0.4 g / cm³ or less, or 0.3 g / cm³ or less. The process may include blowing the composition to produce an article or part comprising the thermoplastic copolyester elastomer foam. In some instances, the process for forming the thermoplastic copolyester elastomer foam comprises injection molding a mixture comprising the composition described herein and a supercritical fluid (e.g., supercritical carbon dioxide or supercritical nitrogen) in a mold, and removing the thermoplastic copolyester elastomer foam from the mold.

[0192] In some aspects, the disclosed foamed polymeric materials may also include one or more thermoplastic polyurethanes, such as Fortimopolymer. TM (Mitsui Chemicals, Inc., Tokyo, Japan); (Covestro LLC, Pittsburgh, Pennsylvania, USA); and BounCell-X TM (Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA).

[0193] In some aspects, the disclosed foamed polymeric material may further include one or more olefin polymers. The olefin polymers may include ethylene-based copolymers, propylene-based copolymers, and butene-based copolymers. In some aspects, the olefin polymers are ethylene-based copolymers, such as styrene-ethylene / butene-styrene (SEBS) copolymers; ethylene-propylene diene monomer (EPDM) copolymers; ethylene-vinyl acetate (EVA) copolymers; ethylene alkyl acrylate (EAA) copolymers; ethylene alkyl methacrylate (EAMA) copolymers; any copolymers thereof; and any blends thereof. In some aspects, the ratio V of the total weight parts of the olefin polymers present in the composition to the total weight parts of the thermoplastic copolyester elastomer in the composition is about 0.0 to about 0.6, about 0.0 to about 0.4, about 0.01 to about 0.4, or about 0.01 to about 0.6, or about 0.1 to about 0.4.

[0194] In some aspects, the disclosed foamed polymeric material may also include an ethylene-vinyl acetate (EVA) copolymer. The ethylene-vinyl acetate (EVA) copolymer may have a range of vinyl acetate contents, for example, about 50 percent to about 90 percent, about 50 percent to about 80 percent, about 5 percent to about 50 percent, about 10 percent to about 45 percent, about 10 percent to about 30 percent, about 30 percent to about 45 percent, or about 20 percent to about 35 percent.

[0195] additive.

[0196] In several aspects, the disclosed foamed polymer materials may also independently contain additives. Additives may be directly incorporated into the disclosed foam particles or binders, or optionally applied to the disclosed foam particles or binders. Additives that may be used in the disclosed foam particles or binders include, but are not limited to, dyes, pigments, colorants, UV absorbers, hindered amine light stabilizers, antioxidants, processing aids or processing agents, plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheological additives, catalysts, flow control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke suppressants, flameproofing agents, antistatic agents, fillers, or mixtures of two or more of the foregoing. In some aspects, additives may be waxes, antioxidants, UV absorbers, colorants, or combinations thereof.

[0197] When used, the additive may be present in amounts from about 0.01% by weight to about 10% by weight, from about 0.025% by weight to about 5% by weight, or from about 0.1% by weight to 3% by weight, wherein the weight percentage is based on the sum of the material components in the thermoplastic composition, fiber, filament, yarn, or fabric.

[0198] Individual components can be blended with other components of a thermoplastic composition in a continuous or batch mixer, such as in an intermeshing rotor mixer like an intermix mixer, a twin-screw extruder, a tangential rotor mixer such as a Banbury mixer using a twin-roll mill, or some combination thereof, to produce a composition containing a thermoplastic polymer and additives. The mixer can blend the components together via a single step or multiple steps, and can combine the components via dispersion mixing or distribution mixing to form the resulting thermoplastic composition. This step is often referred to as "compounding".

[0199] In some respects, the additive is an antioxidant, such as ascorbic acid, alkylated monophenols, alkylthiomethylphenols, hydroquinone or alkylated hydroquinones, tocopherols, hydroxylated diphenyl ethers, alkylene bisphenols, benzyl compounds, hydroxylated malonic esters, aromatic hydroxybenzyl compounds, triazine compounds, benzylphosphonates, acylaminophenols, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, amine antioxidants, or mixtures of two or more of the foregoing.

[0200] Exemplary alkylated monophenols include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-ethylcyclohexyl)-4,6-dimethylphenol, 2,6-bis(octadecyl)-4-methylphenol, and 2,4-dimethylphenol. 6-Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols whose side chains are straight or branched, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundecane-1-yl)phenol, 2,4-dimethyl-6-(1-methylheptadecane-1-yl)phenol, 2,4-dimethyl-6-(1-methyltetrazane-1-yl)phenol, and mixtures of two or more of the foregoing.

[0201] Exemplary alkylthiomethylphenols include, but are not limited to, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures of two or more of the foregoing.

[0202] Exemplary hydroquinones and alkylated hydroquinones include, but are not limited to, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and mixtures of two or more of the foregoing.

[0203] Exemplary tocopherols include, but are not limited to, α-tocopherol, p-tocopherol, 7-tocopherol, 6-tocopherol, and mixtures of two or more of the foregoing.

[0204] Exemplary hydroxylated thiodiphenyl ethers include, but are not limited to, 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-disec-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide, and mixtures of two or more of the foregoing.

[0205] Exemplary alkylene bisphenols include, but are not limited to, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), and 2,2'-alkylene bisphenol. 2,2'-Ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-Methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol) 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3-tert-butyl)butane] [2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecyl mercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, and mixtures of two or more of the foregoing.

[0206] Exemplary benzyl compounds include, but are not limited to, 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, and 3,5-di-tert-butyl -4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethyl ester, and mixtures of two or more of the foregoing.

[0207] Exemplary hydroxybenzyl malonates include, but are not limited to, bis(octadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, bis(octadecyl-2-(3-tert-butyl-4-hydroxy-5-ethylbenzyl)malonate, bis(dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and mixtures of two or more of the foregoing.

[0208] Exemplary aromatic hydroxybenzyl compounds include, but are not limited to, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixtures of two or more of the foregoing.

[0209] Exemplary triazine compounds include, but are not limited to, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, and 1,3,5-tris(3 5-Di-tert-butyl-4-hydroxy-benzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, and mixtures of two or more of the foregoing.

[0210] Exemplary benzylphosphonates include, but are not limited to, calcium salts of dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures of two or more of the foregoing.

[0211] Exemplary acylaminophenols include, but are not limited to, 4-hydroxy-lauricoaniline, 4-hydroxy-stearicoaniline, 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, and mixtures of two or more of the foregoing.

[0212] Exemplary esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0213] Exemplary esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0214] Exemplary esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0215] Exemplary esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0216] Exemplary amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide, and mixtures of two or more of the foregoing.

[0217] Exemplary amine antioxidants include, but are not limited to, N,N′-diisopropyl-p-phenylene diamine, N,N′-disec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylene diamine, N,N′-bis(1-methylheptyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N,N′-diphenylp-phenylene diamine, N,N′-bis(2-naphthyl)-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenylp-phenylene diamine, and N-(1-methylheptyl)-N′-phenylp-phenylene diamine. Amines, N-cyclohexyl-N′-phenyl-p-phenylene diamine, 4-(p-toluenesulfonyl)diphenylamine, N,N′-dimethyl-N,N′-disec-butyl-p-phenylene diamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p′-ditert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-ditert-butyl-4-dimethylaminomethylphenol, 2,4 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanidine, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octyl diphenylamine, mixtures of monoalkylated and dialkylated nonyl diphenylamine, mixtures of monoalkylated and dialkylated dodecyl diphenylamine, mixtures of monoalkylated and dialkylated isopropyl diphenylamine / isohexyl diphenylamine, monoalkylated and dialkylated diphenylamine, etc. Mixtures of alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of monoalkylated and dialkylated tert-butylphenothiazine / tert-octylphenothiazine, mixtures of monoalkylated and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperidin-4-yl)-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol, and mixtures of two or more of the foregoing.

[0218] In some respects, the additive is a UV absorber and / or a light stabilizer, including but not limited to 2-(2-hydroxyphenyl)-2H-benzotriazole compounds, 2-hydroxybenzophenone compounds, esters of substituted and unsubstituted benzoic acids, acrylate or malonic acid ester compounds, sterically hindered amine stabilizer compounds, oxamide compounds, triaryl-o-hydroxyphenyl-s-triazine compounds, or mixtures of two or more of the foregoing.

[0219] Exemplary 2-(2-hydroxyphenyl)-2H-benzotriazole compounds include, but are not limited to, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole. 2-(2-hydroxy-4-octoxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-(ω)-hydroxy-octa(ethyleneoxy)carbonyl-ethyl)-phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonyl)ethylphenyl)-2H-benzotriazole, deca- Dialkylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, (2-Ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazole-2-yl)phenol, 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,5-Di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamon Methyl benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and mixtures of two or more of the foregoing.

[0220] Exemplary 2-hydroxybenzophenone compounds include, but are not limited to, 4-hydroxy derivatives, 4-methoxy derivatives, 4-octoxy derivatives, 4-decoxy derivatives, 4-dodecoxy derivatives, 4-benzyloxy derivatives, 4,2′,4′-trihydroxy derivatives and 2′-hydroxy-4,4′-dimethoxy derivatives of 2-hydroxybenzophenone, as well as mixtures of two or more such derivatives.

[0221] Exemplary esters of substituted and unsubstituted benzoic acid include, but are not limited to, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresenol, bis(4-tert-butylbenzoyl)resenol, benzoylresenol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and mixtures of two or more of the foregoing.

[0222] Exemplary acrylate or malonic acid ester compounds include, but are not limited to, ethyl α-cyano-β,β-diphenylacrylate or isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbonylmethoxy-cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbonylmethoxy-p-methoxycinnamate, N-(β-carbonylmethoxy-β-cyanovinyl)-2-methyl-indoline, dimethyl-p-methoxybenzylmalonic acid ester, di(1,2,2,6,6-pentamethylpiperidin-4-yl)-p-methoxybenzylmalonic acid ester, and mixtures of two or more of the foregoing.

[0223] Exemplary sterically hindered amine stabilizer compounds include, but are not limited to, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, and bis(1,2,2,6,6-pentamethyl-4-piperidine). 1,2,2,6,6-Tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantoin triacetate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane-tetracarboxylic acid ester, 1,1′-(1,2- Ethylenediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyl-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione, bis (1-Octoxy-2,2,6,6-Tetramethylpiperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-piperidinyl) succinate, straight-chain or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4].5] Dec-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3 ,8-diaza-4-oxo-spiro[4,5]decane, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl Piperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate, and 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine, and mixtures of two or more of the foregoing.

[0224] Exemplary oxamide compounds include, but are not limited to, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-bis(dodecyloxy-5,5′-di-tert-butoxanilide, 2-ethyl Oxy-2′-ethyloxalaniline, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethyloxalaniline and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxalaniline, mixtures of o-methoxydisubstituted oxalaniline and p-methoxydisubstituted oxalaniline, mixtures of o-ethoxydisubstituted oxalaniline and p-ethoxydisubstituted oxalaniline, and mixtures of two or more of the foregoing.

[0225] Exemplary triaryl-o-hydroxyphenyl-s-triazine compounds include, but are not limited to, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-octoxyphenyl)-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, and 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl) 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-biphenyl)-6-(2-hydroxy-4-octyloxycarbonylethyleneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl]-6-2-hydroxy-4-(3-sec-pentoxy-2- [2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butoxyphenyl)-6-(2,4-di-n-butoxyphenyl)-s-triazine, methylenebis{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)-phenyl]-s-triazine}, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6- (2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine, 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine, and mixtures of two or more of the foregoing.

[0226] In some respects, the additive is a peroxide scavenger, such as esters of β-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl ester, or tridecyl ester; mercaptobenzimidazole; and zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, or mixtures thereof.

[0227] In some respects, the additives are polyamide stabilizers, such as halogens like copper salts of iodine, and / or phosphorus compounds and salts of divalent manganese.

[0228] In some cases, the additives are alkaline stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.

[0229] In some aspects, the disclosed foamed polymer materials may also include one or more nucleating agents. Nucleating agents are widely used to modify the properties of a variety of polymers. Nucleating agents can help reduce foam density, increase the number of pores present in the foam, and reduce the pore size in the foam by providing a surface for heterogeneous nucleation of bubbles from a supercritical fluid state. For the thermoplastic copolyester elastomer foam of this disclosure, the nucleating agent can affect the properties of the final foam article by altering the amount, distribution, and rate of supercritical fluid conversion from liquid to gas during a foaming process at lower pressures. The addition of the nucleating agent provides a surface on which the supercritical fluid can convert from liquid to gas. Therefore, numerous nucleation sites will result in numerous pore domains. In specific instances, the nucleating agent may include a metal salt of a fatty acid. In some aspects, the nucleating agent is zinc stearate. In some aspects, the composition comprises a nucleating agent in amounts of about 0.1 wt. percent to about 10 wt. percent, about 0.1 wt. percent to about 5 wt. percent, about 0.1 wt. percent to about 2 wt. percent, or about 0.5 wt. percent to about 2 wt. percent based on the total weight of the composition.

[0230] In some aspects, the additive is a nucleating agent, such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates, or sulfates of alkaline earth metals, or mixtures thereof. Alternatively, the nucleating agent can be a monocarboxylic acid or polycarboxylic acid and its salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, sodium benzoate, or mixtures thereof. In other aspects, the additive can be a nucleating agent comprising both inorganic and organic materials as disclosed herein.

[0231] In some respects, rheological modifiers can be nanoparticles, nanoclays, nanocarbons, graphite, nanosilica, and the like with a fairly high aspect ratio.

[0232] In another aspect, the foamed polymer material may also include a filler. The filler may be present in an amount from about 0.05% to about 20% by weight of the total weight of the foamed polymer material, or from about 0.1% to about 10% by weight of the total weight of the foamed polymer material; or in an amount of values ​​within the aforementioned ranges or a set of values, or in an amount within any range of subsets of the aforementioned ranges. In some cases, the filler is a particulate filler. In another aspect, the filler is a carbonaceous filler. The carbonaceous filler may be carbon black, activated carbon, graphite, carbon fibers, carbon protofibrils, carbon nanoparticles, or combinations thereof. In several aspects, the carbonaceous filler may be chemically modified. Alternatively, the filler may be an inorganic filler. Inorganic fillers may be oxides, hydroxides, salts, silicates, metals, or combinations thereof. Examples of inorganic fillers include, but are not limited to, glass spheres, glass fibers, hollow glass spheres, glass sheets, MgO, SiO2, Sb2O3, Al2O3, ZnO, talc, mica, kaolin, wollastonite, or combinations thereof.

[0233] In some applications, additives are fillers or reinforcing agents, such as clay, kaolin, talc, asbestos, graphite, and glass (such as glass fiber, glass particles, and glass bubbles). Bulbs, glass spheres or glass-like spheres, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates (such as calcium carbonate, magnesium carbonate and the like), metals (such as titanium, tungsten, zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt, beryllium and alloys thereof), metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like), metal hydroxides, granular synthetic plastics (such as high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide and the like), synthetic fibers (such as fibers containing high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide and the like), granular carbonaceous materials (such as carbon black and the like), powders or fibers of wood flour and other natural products, as well as cotton lint, cellulose lint, cellulose pulp, leather fibers, and combinations thereof. Non-limiting examples of heavy filler components that can be used to increase the specific gravity of cured elastomeric compositions may include titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze, cobalt, beryllium, zinc, tin, metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, and zirconium oxide), metal sulfates (such as barium sulfate), metal carbonates (such as calcium carbonate), and combinations thereof. Non-limiting examples of light filler components that can be used to reduce the specific gravity of elastomeric compounds may include granular plastics, hollow glass spheres, ceramics and hollow spheres, re-ground materials, and foams, which may be used in combination.

[0234] In some instances, the disclosed foamed polymer materials may also include nanofillers. Nanofillers can function not only as mechanical reinforcing agents but also as nucleating agents. Various nanofillers can be used in place of zinc stearate or in addition to zinc stearate. Nanofillers can include nanomaterials having one-dimensional structures such as plates, sheets, and / or shells; two-dimensional structures such as nanotubes and nanofibers with diameters less than 0.1 μm; or three-dimensional nanostructures such as nanoparticles or beads. Nanosheet fillers can be natural or synthetic clays, as well as phosphates of transition metals. Clay-based nanocomposites produce an overall improvement in physical properties. The most widely used nanofiller is phyllosilicate. Nanofillers can include nano-oxides, such as titanium dioxide or rutile nanoparticles. Other nanofillers can include alumina or aluminum oxide nanoparticles, diatomaceous earth, and nanoscale carbon materials such as single-walled carbon nanotubes (SWCNTs) or double-walled carbon nanotubes (DWCNTs).

[0235] In some aspects, the additive is a crosslinking agent. A variety of crosslinking agents are available that can be used in the disclosed thermoplastic compositions. For example, the crosslinking agent can be a free radical initiator. Free radical initiators can generate free radicals through thermal decomposition or UV radiation. Free radical initiators can be present in amounts from about 0.001 weight percent to about 1.0 weight percent. Various free radical initiators can be used as free radical sources to produce thermoplastic compositions having a crosslinked structure. Suitable free radical initiators applied include peroxides, sulfur, and sulfides. Exemplary peroxides include, but are not limited to, aliphatic and aromatic peroxides, such as diacetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(butylperoxy)-3-hexyne, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 1,4-bis(tert-butylperoxyisopropyl)benzene, tert-butylperoxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and bis(2,4-dichlorobenzoyl), or combinations of two or more of the foregoing.

[0236] In some aspects, the additive is a colorant. As used herein, the term "colorant" refers to a compound that provides color to a substrate, such as the disclosed thermoplastic composition. The colorant can be an organic pigment or an inorganic pigment, dye, or a mixture or combination thereof. In other aspects, the pigment or dye is an inorganic material such as a metal oxide, such as iron oxide or titanium dioxide. Alternatively, the inorganic pigment or dye can be a metal compound such as strontium chromate or barium sulfate, or a metallic pigment such as aluminum flakes or aluminum particles. Other exemplary inorganic pigments include carbon black, talc, and the like. In some cases, the metal compound is not a cadmium-containing metal compound. In some cases, it may be desirable that the inorganic pigment or dye is not an inorganic pigment or dye containing lead compounds, cadmium compounds, and chromium (VI) compounds. In other aspects, the pigment or dye is an organic compound such as perylene, phthalocyanine derivatives (e.g., copper phthalocyanine), indoanthraquinone, benzimidazolone, quinacridone, perinone, and methylimino derivatives. For example, the colorant can be added to the thermoplastic composition directly or otherwise via a masterbatch in a mixing apparatus such as an extruder. In several aspects, the disclosed thermoplastic composition can be constituted in a weight percentage between about 0.005 and about 5% relative to the weight of the composition. In another aspect, the disclosed thermoplastic composition can be constituted in a weight percentage between about 0.01 and about 3% relative to the weight of the composition.

[0237] The disclosed foamed polymer material may contain one or more colorants. In some aspects, the disclosed foamed polymer material may contain a first colorant, and the binding material may contain a second colorant. In this case, it should be understood that the first colorant may include one or more dyes or pigments. Similarly, it should be understood that the second colorant may include one or more dyes or pigments.

[0238] There are at least two types of metal complex dyes that can be used as colorants. Acidic metal complex dyes are soluble in water and are therefore dissolved in an aqueous solvent system before use. Solvent-based metal complex dyes are insoluble in water and are therefore dissolved in an aqueous / organic solvent system before use.

[0239] Solvent systems for metal complex dyes should both dissolve the dye and facilitate the diffusion of dye molecules into the elastomer matrix under mild conditions. Therefore, it has been found that certain organic solvents not only dissolve water-insoluble dyes, such as solvent metal complex dyes, but also promote or facilitate the diffusion of dyes into the polymer matrices of both acid metal complex dyes and solvent metal complex dyes.

[0240] Suitable organic solvents include ethylene glycol phenyl ether (EGPE) and isopropanol. Relatively small amounts of organic solvent are typically required.

[0241] Suitable solvent systems for acid metal complex dyes comprise, for example, 90 to 100 vol percent water and 0 to 10 vol percent organic solvent. Typical amounts of organic solvent are 0.5 to 7 vol percent or 1 to 5 vol percent.

[0242] Suitable solvent systems for solvent-metal complex dyes include a third component, typically an organic solvent, in addition to water and ethylene glycol phenyl ether, to increase the dye's solubility. For example, the solvent system may contain 40 to 80 vol% water and 60 to 20 vol% organic solvent. Suitable organic solvents include, but are not limited to, alcohols, ethers, esters, and ketones. Suitable solvent-metal complex dyes include Orasol Yellow 2RLN, OrasolYellow2GLN-M, Pylam Solvent Red, Pylam Brilliant Yellow, and Resofast Orange M2Y.

[0243] Alternatively, a two-phase solvent system can be used, wherein the dye is soluble in an organic solvent but insoluble in water, and the organic solvent is only partially miscible with water or insoluble or practically insoluble in water. Suitable organic solvents for forming a two-phase system include polar organic solvents that are insoluble in water, such as suitable hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, amides, acids, and halogenated compounds. Examples include, but are not limited to, n-butanol, cyclohexanol, butyl acetate, and ethylene glycol phenyl ether.

[0244] In a two-phase solvent system, a solution containing a large amount of water and a small amount of organic solvent is prepared. The organic solvent is partially miscible with water or almost insoluble in water, thus forming a two-phase system. This two-phase solvent composition allows for rapid and uniform dyeing, for example, of foam particles.

[0245] The dye can first be dissolved in an organic solvent to form a homogeneous solution, and then the solution can be dispersed as droplets in water under agitation or stirring. Alternatively, the organic solvent can be combined with water to form a two-phase solvent. The dye is then added to the two-phase solvent under agitation or stirring to form droplets.

[0246] Two-phase solvent compositions may contain 1 to 30 volume percent, for example 1 to 25 volume percent, of an organic solvent and 70 to 99 volume percent, for example 75 to 99 volume percent, of water. These two-phase solvent compositions are particularly suitable for solvent dyes that have high solubility in organic solvents. Typically, dyes suitable for use in this embodiment include dyes that are highly soluble in organic solvents but practically insoluble in water.

[0247] When a suitable substrate is immersed in a two-phase solvent-dye system, droplets of both organic solvent and dye are preferentially adsorbed onto the substrate surface. This creates a thin layer of organic solvent with a high concentration of dye on the substrate surface. Furthermore, the organic solvent causes the substrate to swell, providing an open polymer structure. This combination of an open structure in the substrate and a high concentration of dye facilitates rapid diffusion of dye molecules into the substrate.

[0248] Therefore, the two-phase solvent composition both dissolves the dye and facilitates the diffusion of dye molecules into the flexible substrate under mild conditions. Compared to conventional dyeing systems, the two-phase solvent dye system offers rapid dyeing, uses less organic solvent, employs mild dyeing conditions, and provides the potential for efficient dye recovery / removal from the solvent.

[0249] In some respects, the dye can be a metal complex dye, such as, but not limited to, Bezanyl Black, Bezanyl Red, Bezanyl Yellow, Orasol Black, Orasol Blue GN, Orasol Red G, Orasol Yellow 2GLN, Isolan Blue, SP-R, Isolan Grey SP-G, Isolan Red SP-G, Isolan Yellow SP-2RL, Pylam Solvent Blue, Pylam Solvent Red, Pylam Solvent Yellow, Resofast Blue, Resofast Orange, and Resofast Yellow.

[0250] In some aspects, the disclosed foamed polymeric material may be dyed with nonionic or anionic (“acidic”) dyes by: (1) before injection of a supercritical fluid, (2) during injection of a supercritical fluid by dissolving or dispersing a nonionic or anionic dye in the supercritical fluid, which optionally contains a polar liquid, (3) during immersion in a heated fluid containing the dye, or (4) after foaming.

[0251] In some applications, colorants can be acid dyes, such as water-soluble anionic dyes. A wide variety of acid dyes are available, ranging from dull tones to brilliant shades. Chemically, acid dyes include azo compounds, anthraquinone compounds, and triarylmethane compounds.

[0252] The Color Index (CI), jointly published by the Society of Dyers and Colourists (UK) and the American Association of Textile Chemists and Colorists (USA), is a comprehensive compilation of the most extensive range of dyes and pigments for large-scale coloring purposes, encompassing 12,000 products under 2,000 CI common names. In the CI, each compound is provided with two numbers, referring to both its color classification and chemical classification. The "common name" indicates the application area and / or coloring method, while the other number is the "constitution number." Non-limiting examples of acid dyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110, 116, 127, 151, 158, 1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246, and 250; Acid Red 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183, 184, 186, and 1 94, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278, 283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419 and 447; Acid Violet 3, 5, 7, 17, 54, 90 and 92; Acid Brown 4, 14, 15, 45, 50, 58, 75, 97, 98, 147, 160: 1, 161, 165, 191, 235, 239, 248, 282, 283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414, 420, 422, 425, 432 and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61, 67, 74, 80, 86, 94, 139, 142, 144, 154 and 162 Acid Blue 1, 7, 9, 15, 92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green 1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60, 64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, and 235, and combinations thereof. Acid dyes can be used alone or in any combination in dye solutions.

[0253] Acid dyes and nonionic disperse dyes are commercially available from a number of sources, including Dystar LP, Charlotte, North Carolina, under the trademark TELON; Huntsman Corporation, Woodlands, Texas, under the trademarks ERIONYL and TECTILON; BASF SE, Ludwigshafen, Germany, under the trademark BASACID; Clariant International Ltd., Muttenz, Switzerland, under the trademarks SOLVAPERM, HOSTASOL, POLYSYNTHREN, and SAVINYL; and Bezema AG, Montlingen, Switzerland, under the trade name Bemacid.

[0254] Nonionic disperse dyes are also commercially available in many colors, including fluorescent dyes.

[0255] In some aspects, the disclosed foamed polymer material can be dyed prior to foaming. The acidic disperse dye solution or nonionic disperse dye solution in which the spheres or other articles are dyed can comprise, for example, from about 0.001 g / L to about 5.0 g / L, preferably from about 0.01 g / L to about 2 g / L, an acidic disperse dye compound or a combination of acidic disperse dye compounds or nonionic disperse dye compounds. The amount of acidic disperse dye compound or nonionic disperse dye compound used will determine how strong the color is and how quickly the spheres or other articles are dyed, and can be optimized in a direct manner; generally, a more concentrated dye solution can provide a stronger (deeper, darker, more intense) dyeing color and can dye spheres or other articles containing thermoplastic elastomers more quickly.

[0256] Dye solutions may include water-soluble organic solvents. The water solubility of a particular organic solvent used in a specific amount in the dye solution is determined by the concentration at 20°C and 1 atm pressure in the alcohol used in the dye solution; an organic solvent is water-soluble if it is completely soluble or completely miscible in water at a concentration at 20°C and 1 atm pressure in the alcohol used in the dye solution and does not form any separate phase or layer. Suitable non-limiting examples of water-soluble organic solvents that may be used include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and glycerol; ketones such as acetone and methyl ethyl ketone; esters such as butyl acetate, which is soluble in water in limited amounts; and ethylene glycol ethers and ethylene glycol ether esters (especially acetate esters), such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Water-soluble organic solvents may be contained in concentrations of up to about 50 percent, or up to about 25 percent, or from about 1 percent to about 50 percent, or from about 5 percent to about 40 percent, or from about 10 percent to about 30 percent, or from about 15 percent to about 25 percent by volume, of the aqueous medium used to manufacture the dye solution. Whether and how much organic solvent is used may vary depending on the type of dye used and the application method used to contact the dye solution with the pellets or other articles.

[0257] If the disclosed foamed polymer material comprises a thermoplastic polyurethane elastomer or a thermoplastic polyurea elastomer, the anionic dye solution also advantageously comprises a quaternary (tetraalkyl)ammonium salt selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds. Such articles are advantageously dyed in an acidic dye solution comprising an anionic dye compound, a quaternary ammonium salt selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds, and optionally a water-soluble organic solvent.

[0258] The counterion of the quaternary ammonium salt should be selected such that the quaternary ammonium salt forms a stable solution with the anionic dye. The quaternary ammonium compound can be, for example, a halide (such as chloride, bromide, or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate, chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite, hexafluorophosphite, borate, tetrafluoroborate, cyanide, isocyanate, azide, thiosulfate, thiocyanate, or carboxylate (such as acetate or oxalate). In some embodiments, the anion of a weaker Lewis base can be selected for the tetraalkylammonium compound to produce a darker color for use in a cover layer or coating for dyeing. In many embodiments, the tetraalkylammonium compound is or includes tetrabutylammonium halide or tetrahexylammonium halide, particularly tetrabutylammonium bromide or tetrabutylammonium chloride or tetrahexylammonium bromide or tetrahexylammonium chloride.

[0259] When the disclosed foamed polymer material comprises thermoplastic polyurethane elastomer or thermoplastic polyurea elastomer, the acidic dye solution used to dye the disclosed foamed polymer material may contain from about 0.1 equivalents to about 5 equivalents of a soluble tetraalkylammonium compound per equivalent of dye compound. In various embodiments, the acidic dye solution may contain from about 0.5 equivalents to about 4 equivalents, preferably from about 1 equivalent to about 4 equivalents of a tetraalkylammonium compound per equivalent of dye compound. The amount of tetraalkylammonium compound used with a particular acidic dye compound depends on the rate at which the dye diffuses into and within the capping or coating layer, and can be optimized in a direct manner. The process of dyeing the disclosed foamed polymer material comprising thermoplastic polyurethane elastomer or thermoplastic polyurea elastomer with this dye solution containing a soluble tetraalkylammonium compound can produce strong color intensity in the dyed foam particles or bonding materials.

[0260] The disclosed foamed polymer material can be dyed with nonionic or anionic dyes prior to the infusion of a supercritical fluid. The microspheres can also be dyed simultaneously with the infusion of the supercritical fluid by dissolving or dispersing a nonionic or anionic dye in the supercritical fluid, which optionally contains a polar liquid. The microspheres can also be dyed while immersed in a heated fluid containing a dye. Specifically, the heated fluid can be a heated aqueous dye solution, which may contain quaternary ammonium salts and organic solvents as described. Finally, the disclosed foamed polymer material can be dyed after foaming using a dyeing process as described.

[0261] Methods for representing disclosed items.

[0262] Several methods exist in the art for measuring the elasticity and / or energy return of foam. One method for measuring the elasticity of foam is based on ASTM D 2632-92, a test for solid rubber materials. For use with foam, the test sample is prepared as described in ASTM D2632-92, but a foam sample is used instead of a solid rubber sample. The test uses a plunger that is guided by a vertical rod and dropped from a height onto the test sample. The drop height is divided into 100 equal parts, and the height of the plunger's rebound is measured using this 100-part scale to determine the elasticity of the sample. Alternative methods can also be used, which employ a ball of standard weight dropped onto the sample and measure the ball's rebound height to determine the sample's elasticity. In some aspects, force / displacement behavior is used to determine the elasticity and / or energy return, the force / displacement behavior being determined using methods known to those skilled in the art.

[0263] In several aspects, the force / displacement behavior of the disclosed articles can be measured using an Instron Electropuls E10000 (Instron, Norwood, Massachusetts, USA) with a stainless steel 45mm circular cross-section impact geometry. The test foam board can be approximately 10mm thick, although thinner or thicker foam boards can also be used. Each sample can be evaluated using two different compression cycles: a “run” and a “walk.” The “run” compression cycle consists of the sample being compressed from 0 Newtons to 300 Newtons and back to 0 Newtons within 180 milliseconds under displacement control, followed by a 400-millisecond pause, totaling ~1.7 Hz. The “walk” compression cycle consists of the sample being compressed from 0 Newtons to 144 Newtons and back to 0 Newtons within 600 milliseconds, followed by a 400-millisecond pause, totaling ~1 Hz.

[0264] Compression can be measured by preparing samples of foam with a standard thickness (e.g., 10 mm). Samples with a thickness less than the standard can be stacked to create a sample with a standard thickness. The sample is loaded into a metal compression plate and compressed to a height of 50 percent of the original thickness (e.g., 5 mm). The sample is placed in an oven at 50 degrees Celsius with its sides facing down for 6 hours. At the end of 6 hours, the sample is removed from the oven and from the metal compression plate and allowed to cool for 30 minutes. After cooling, the thickness of the sample is measured. The percentage of compression deformation (CS) is calculated by: (a) subtracting the final sample thickness from the original sample thickness, and (b) subtracting 50 percent of the compressed thickness from the original sample thickness, (c) dividing (a) by (b), and (d) multiplying the result by 100 to obtain the percentage of compression deformation (where all thicknesses are measured in millimeters).

[0265] Energy input can be viewed as the integral of the force-displacement curve during compressive loading. Hysteresis is considered as a ratio: (energy output) / (energy input), which can also be viewed as the energy efficiency of the foam. Fatigue behavior is judged by the change in foam displacement at the maximum load of the cycle. All properties—stiffness, hysteresis, and fatigue—are measured over multiple cycles for both running and walking compression cycles. A typical characterization using the compression sequence described above can run for 5000 cycles, simulating approximately ~5-10 miles of walking / running, and taking about 45 minutes of testing time on an Instron Electropuls E10000 instrument. Longer runs of up to 100,000 compression cycles can be performed to simulate the accelerated material response used at ~100-200 miles.

[0266] Tensile strength can be measured on a punched sample of a dumbbell-shaped article of standard dimensions, such as a width of 2.5 cm, a length of 11.5 cm, and a minimum thickness of 3 mm to 4 mm. The dumbbell conforms to the shape described in ASTM D412, Die C. The sample is symmetrically loaded into a long-stroke extensometer such as the Instron 2603-080 and tested using this long-stroke extensometer, which allows for a minimum of 1000 percent strain, with a gauge length of 25 mm and a resolution of at least 0.1 mm. The tensile value at the failure point of the sample (the point at which the load value initially falls during the test) is recorded.

[0267] Unless expressly stated otherwise, it is not intended that any method described herein require its steps to be performed in a particular order. Therefore, no order is intended to be inferred in any respect where a method claim does not actually describe the order in which its steps are followed, or where the claims or specification do not specifically state that these steps are restricted to a particular order. This applies to any possible non-express basis of interpretation, including: logical questions concerning the arrangement of steps or the flow of operations; simple meanings derived from grammatical organization or punctuation; and

[0268] definition

[0269] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will also be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having the meaning consistent with their meaning in the context of the specification and in the relevant field, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0270] The terms “comprises,” “comprising,” “including,” and “having” are inclusive and therefore specify the presence of a feature, step, operation, element, and / or component, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0271] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural indicators. Thus, for example, references to “foam particles,” “sole interlayer,” or “adhesive” include, but are not limited to, two or more such foam particles, sole interlayers, or adhesives and the like.

[0272] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0273] As used herein, substantially means at least 50 percent, 60 percent, 75 percent, 90 percent, 95 percent or more, as determined based on weight or volume.

[0274] The terms first, second, third, etc., may be used herein to describe different elements, components, regions, layers, and / or segments. These elements, components, regions, layers, and / or segments should not be limited by these terms. These terms may be used only to distinguish one element, component, region, layer, or segment from another. Terms such as “first,” “second,” and other numerical terms do not imply a sequence or order unless the context clearly indicates otherwise. Therefore, the first element, first component, first region, first layer, or first segment discussed below may be referred to as a second element, second component, second region, second layer, or second segment without departing from the teachings of the embodiment configuration.

[0275] As used herein, the modifiers “up,” “down,” “top,” “bottom,” “upward,” “downward,” “vertical,” “horizontal,” “longitudinal,” “lateral,” “front,” “back,” etc., unless otherwise defined or clearly stated from this disclosure, are relative terms referring to the various structures or orientations of footwear placed in the context of footwear worn by a user standing on a flat, horizontal surface.

[0276] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. Where a stated range contains one or both extreme values, the range excluding any one or both of those extreme values ​​is also included in this disclosure; for example, the phrase “x to y” includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. Ranges may also be expressed as upper limits, such as 'about x, y, z, or less' and should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'less than x', 'less than y', and 'less than z'. Similarly, the phrase 'about x, y, z, or greater' should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'greater than x', 'greater than y', and 'greater than z'. Furthermore, the phrase “about 'x' to 'y'”, where 'x' and 'y' are numerical values, includes “about 'x' to about 'y'”. It should be understood that this range format is used for convenience and brevity, and therefore should be interpreted flexibly to include not only the values ​​explicitly stated as extreme values ​​of the range, but also all individual values ​​or subranges covered within that range, as if each value and subrange were explicitly stated. For example, the range of numbers “about 0.1 percent to 5 percent” should be interpreted to include not only the explicitly stated values ​​of about 0.1 percent to about 5 percent, but also the individual values ​​(e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and subranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent, and 4.4 percent) within the indicated range.

[0277] As used herein, the terms “about,” “approximate,” “at or about,” and “generally” mean that the quantity or value in question can be an exact value or a value that provides an equivalent result or effect to that described in the claims or taught herein. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, resulting in an equivalent result or effect. In some cases, the value providing an equivalent result or effect cannot be reasonably determined. In such cases, it should generally be understood that, as used herein, “about” and “at or about” mean a nominal value indicated plus or minus 10 percent variation, unless otherwise indicated or inferred. Generally, quantities, sizes, formulations, parameters, or other quantities or characteristics are “about,” “approximately,” or “at or about,” whether or not explicitly stated as such. It should be understood that when “about,” “approximately,” or “in or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless otherwise specifically stated.

[0278] The term "chemical compound" refers to one or more molecules of a chemical compound, not just a single molecule. Furthermore, the one or more molecules may or may not be identical, as long as they fall under the category of chemical compound. Thus, for example, "polyamide" is interpreted as including one or more polymer molecules of polyamide, where the polymer molecules may or may not be identical (e.g., different molecular weights and / or isomers).

[0279] The terms "at least one" and "one or more" are used interchangeably and have the same meaning, including both single and multiple elements, and may also be indicated by a suffix (one or more) at the end of the element. For example, "at least one polyamide," "one or more polyamides," and "(one or more) polyamides" are used interchangeably and have the same meaning.

[0280] As used herein, the terms “optional” or “optionally” mean that a component, event, or condition described below may or may not occur, and the description includes both cases in which said component, event, or condition occurs and cases in which said component, event, or condition does not occur.

[0281] When used in the claims, the term "receive," such as in "receive uppers for footwear articles," is not intended to require any specific delivery or receipt of the received items. Rather, the term "receive" is used merely to describe items that will be referred to in subsequent elements of the claims for clarity and readability purposes.

[0282] As used herein, the terms “percentage by weight,” “weight percentage,” “wt%,” and “wt.%”, which may be used interchangeably, indicate the weight percentage of a given component based on the total weight of the composition or article, unless otherwise indicated. That is, unless otherwise indicated, all weight percentage values ​​are based on the total weight of the composition. It should be understood that the sum of the weight percentage values ​​of all components in the disclosed composition or formulation is equal to 100.

[0283] Similarly, the terms "percentage by volume," "vol%," and "vol.%" which may be used interchangeably, indicate a percentage by volume of a given component based on the total volume of the composition or article, unless otherwise specified. That is, unless otherwise specified, all volume percentage values ​​are based on the total volume of the composition or article. It should be understood that the sum of the volume percentage values ​​of all components in the disclosed composition, formulation, or article equals 100.

[0284] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the attachment point for a substituent. For example, -CHO is attached by the carbonyl group. Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0285] As used herein, the term "effective amount" refers to an amount sufficient to achieve the desired change in the physical properties of a composition or material. For example, an "effective amount" of filler refers to an amount sufficient to achieve the desired improvement in properties regulated by the formulation components, such as achieving a desired modulus level. The specific level of the composition as an effective amount (by weight percentage) will depend on a variety of factors, including the amount and type of polymer, the amount and type of filler, and the end use of the article made using the composition.

[0286] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes both scenarios in which the event or situation occurs and scenarios in which the event or situation does not occur.

[0287] As used herein, the term "unit" can be used to refer to a single (co)monomer unit, such that, for example, a styrene repeating unit refers to a single styrene (co)monomer unit in the polymer. Furthermore, the term "unit" can be used to refer to a polymer block unit, such that, for example, "styrene repeating unit" can also refer to a polystyrene block; "polyethylene unit" refers to a polyethylene block unit; "polypropylene unit" refers to a polypropylene block unit; "polybutene unit" refers to a polybutene block unit, and so on. Such usage will be clear from the context.

[0288] The term "polymer" refers to a polymer having two or more monomeric substances, and includes terpolymers (i.e. copolymers having three monomeric substances).

[0289] Unless otherwise specified, the temperatures mentioned in this article are determined at standard atmospheric pressure (i.e., 1 atm).

[0290] The components used to prepare the compositions of the present invention and the compositions themselves used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that while specific references cannot be explicitly disclosed for every variety of individual and collective combinations and arrangements of these materials, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and many modifications that can be made to a number of molecules including that compound are discussed, then each and every combination and arrangement of that compound, and possible modifications, are specifically contemplated unless otherwise specifically indicated. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and examples of the combination molecule AD are disclosed, then even though each is not described individually, each is considered to be a combination of meanings contemplated individually and collectively, and thus AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups of AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including but not limited to the steps in methods of making and using the compositions of the present invention. Therefore, if there are multiple additional steps that can be performed, it should be understood that each of these additional steps can be performed using any particular aspect or combination of aspects of the method of the present invention.

[0291] As used herein, the term "alkyl group" refers to a branched or unbranched saturated hydrocarbon group having 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetradecyl, and similar groups. "Lower alkyl" groups are alkyl groups containing 1 to 6 carbon atoms.

[0292] As used herein, the term "aryl group" refers to any carbon-based aromatic group, including but not limited to benzene, naphthalene, etc. The term "aromatic" also includes "heteroaryl group," which is defined as an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted by one or more groups, including but not limited to alkyl, alkynyl, alkenyl, aryl, halides, nitro, amino, esters, ketones, aldehydes, hydroxyl, carboxylic acids, or alkoxy groups.

[0293] As used herein, the term "aralkyl" refers to an aryl group having an alkyl group, alkynyl group, or alkenyl group as defined above attached to an aromatic group. An example of an aralkyl group is a benzyl group.

[0294] The term "organic residue" is defined as a carbon-containing residue, that is, a residue containing at least one carbon atom, and includes, but is not limited to, carbon-containing groups, residues, or groups defined above. Organic residues may contain various heteroatoms, or may be bonded to another molecule via heteroatoms, including oxygen, nitrogen, sulfur, phosphorus, or similar heteroatoms. Examples of organic residues include, but are not limited to, alkyl or substituted alkyl groups, alkoxy or substituted alkoxy groups, monosubstituted or disubstituted amino groups, amide groups, etc. Organic residues may preferably contain 1 to 18 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In another aspect, organic residues may contain 2 to 18 carbon atoms, 2 to 15 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

[0295] A very close synonym for the term "residue" is the term "radical," which, as used in the specification and concluding claims, refers to a fragment, group, or substructure of the molecule described herein, regardless of how the molecule is prepared. For example, the 2,4-dihydroxyphenyl group in a particular compound has the following structure:

[0296]

[0297] Regardless of whether 2,4-dihydroxyphenyl is used to prepare the compound. In some aspects, the group (e.g., alkyl) may be further modified by having one or more "substituent groups" bonded to it (i.e., substituted alkyl groups). The number of atoms in a given group is not critical to the invention unless otherwise indicated herein.

[0298] As used in this article, the terms "number-average molecular weight" or "M" are used... n "Can be used interchangeably, and refers to the statistical average molecular weight of all polymer chains in the sample, and is defined by the following formula:

[0299]

[0300] Where M i It is the molecular weight of the chain and N i This refers to the number of chains at that molecular weight. The M of a polymer, such as a polycarbonate polymer, can be determined using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards, by methods well known to those skilled in the art. n .

[0301] aspect.

[0302] The following list of exemplary aspects supports and is supported by the disclosures provided herein.

[0303] Aspect 1. A thermoplastic copolyester elastomer composition comprising: a thermoplastic copolyester elastomer comprising: (a) more than one first segment, each first segment being derived from a dihydroxy-terminated polydiol; (b) more than one second segment, each second segment being derived from a diol; and (c) more than one third segment, each third segment being derived from an aromatic dicarboxylic acid.

[0304] Aspect 2. The thermoplastic copolyester elastomer composition as described in aspect 1, wherein the thermoplastic copolyester elastomer is a block copolymer; a segment copolymer; a random copolymer; or a condensation copolymer.

[0305] Aspect 3. The thermoplastic copolyester elastomer composition as described in aspect 1 or aspect 2, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of about 50,000 Daltons to about 1,000,000 Daltons.

[0306] Aspect 4. The thermoplastic copolyester elastomer composition as described in aspect 3, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of about 50,000 Daltons to about 500,000 Daltons; about 75,000 Daltons to about 300,000 Daltons; or about 100,000 Daltons to about 200,000 Daltons.

[0307] Aspect 5. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-4, wherein the thermoplastic copolyester elastomer has a first segment to third segment ratio from about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment.

[0308] Aspect 6. The thermoplastic copolyester elastomer composition as described in aspect 5, wherein the thermoplastic copolyester elastomer has a first segment to third segment ratio from about 1:1 to about 1:3 or from about 1:1 to about 1:2 based on the weight of each of the first segment and the third segment.

[0309] Aspect 7. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-6, wherein the thermoplastic copolyester elastomer has a second segment to third segment ratio from about 1:1 to about 1:3 based on the weight of each of the second segment and the third segment.

[0310] Aspect 8. The thermoplastic copolyester elastomer composition of aspect 7, wherein the thermoplastic copolyester elastomer has a second segment to third segment ratio from about 1:1 to about 1:2 or from about 1:1 to about 1:1.52 based on the weight of each of the second segment and the third segment.

[0311] Aspect 9. The thermoplastic copolyester elastomer composition of any one of Aspects 1-8, wherein the first segment of the dihydroxy-terminated polydiol comprises a segment derived from a poly(epoxy)diol having a weight-average molecular weight of about 250 Daltons to about 6000 Daltons.

[0312] Aspect 10. The thermoplastic copolyester elastomer composition of aspect 9, wherein the weight-average molecular weight is about 400 Daltons to about 6,000 Daltons; about 350 Daltons to about 5,000 Daltons; or about 500 Daltons to about 3,000 Daltons.

[0313] Aspect 11. The thermoplastic copolyester elastomer composition of any one of Aspects 9-10, wherein the poly(epoxy) glycol is poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; poly(hexamethylene ether) glycol; poly(heptamethylene ether) glycol; poly(octamethylene ether) glycol; poly(nonamethylene ether) glycol; poly(decamethylene ether) glycol; or a mixture thereof.

[0314] Aspect 12. The thermoplastic copolyester elastomer composition as described in aspect 11, wherein the poly(epoxy) glycol is poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; or poly(hexamethylene ether) glycol.

[0315] Aspect 13. The thermoplastic copolyester elastomer composition as described in aspect 11, wherein the poly(epoxy) glycol is poly(tetramethylene ether) glycol.

[0316] Aspect 14. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-13, wherein the second segment derived from the diol comprises a diol having a molecular weight of less than about 250.

[0317] Aspect 15. The thermoplastic copolyester elastomer composition as described in aspect 14, wherein the diol is a C2-C8 diol.

[0318] Aspect 16. The thermoplastic copolyester elastomer composition of aspect 15, wherein the second segment derived from the diol comprises a diol selected from: ethylene glycol; propylene glycol; butanediol; pentanediol; 2-methylpropanediol; 2,2-dimethylpropanediol; hexanediol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof.

[0319] Aspect 17. The thermoplastic copolyester elastomer composition as described in aspect 16, wherein the diol is selected from 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof.

[0320] Aspect 18. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-17, wherein the third segment derived from an aromatic dicarboxylic acid comprises an aromatic C5-C16 dicarboxylic acid.

[0321] Aspect 19. The thermoplastic copolyester elastomer composition as described in aspect 18, wherein the aromatic C5-C16 dicarboxylic acid has a molecular weight of less than about 300 Daltons or from about 120 Daltons to about 200 Daltons.

[0322] Aspect 20. The thermoplastic copolyester elastomer composition as described in aspect 18, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid or derivatives thereof.

[0323] Aspect 21. The thermoplastic copolyester elastomer composition as described in aspect 20, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid or a dimethyl ester derivative thereof.

[0324] Aspect 22. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-21, wherein the thermoplastic copolyester elastomer comprises:

[0325] (a) More than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxyl-terminated polyethylene glycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0326]

[0327] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and

[0328] (b) More than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0329]

[0330] Wherein R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0331] Aspect 23. The thermoplastic copolyester elastomer composition as described in aspect 22, wherein the first copolyester unit has a structure represented by formula 3:

[0332]

[0333] Wherein R is H or methyl; where y is an integer having a value from 1 to 10; where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons.

[0334] Aspect 24. The thermoplastic copolyester elastomer composition as described in aspect 23, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

[0335] Aspect 25. The thermoplastic copolyester elastomer composition as described in aspect 23 or aspect 24, wherein R is hydrogen; wherein R is methyl; wherein R is hydrogen and y is an integer having a value of 1, 2 or 3; or wherein R is methyl and y is an integer having a value of 1.

[0336] Aspect 26. The thermoplastic copolyester elastomer composition as described in aspect 22, wherein the first copolyester unit has a structure represented by formula 4:

[0337]

[0338] Where z is an integer having a value from 2 to 60; and the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons.

[0339] Aspect 27. The thermoplastic copolyester elastomer composition as described in any one of Aspects 23-26, wherein z is an integer having a value from 5 to 60; from 5 to 50; from 5 to 40; from 4 to 30; from 4 to 20; or from 2 to 10.

[0340] Aspect 28. The thermoplastic copolyester elastomer composition of any one of aspects 23-27, wherein the weight-average molecular weight of each of the more than one first copolyester unit is from about 400 Daltons to about 6,000 Daltons; from about 400 Daltons to about 5,000 Daltons; from about 400 Daltons to about 4,000 Daltons; from about 400 Daltons to about 3,000 Daltons; from about 500 Daltons to about 6,000 Daltons; from about 500 Daltons to about 5,000 Daltons; from about 500 Daltons to about 4,000 Daltons; from about 500 Daltons to about 3,000 Daltons; from about 600 Daltons to about 6,000 Daltons; from about 600 Daltons to about 5,000 Daltons; from about 600 Daltons to about 4,000 Daltons; from about 600 Daltons to about 3,000 Daltons.

[0341] Aspect 29. The thermoplastic copolyester elastomer composition as described in any one of Aspects 22-28, wherein the second copolyester unit has a structure represented by Formula 5:

[0342]

[0343] Where x is an integer with values ​​from 1 to 20.

[0344] Aspect 30. The thermoplastic copolyester elastomer composition as described in aspect 29, wherein x is an integer having a value from 2 to 18; a value from 2 to 17; a value from 2 to 16; a value from 2 to 15; a value from 2 to 14; a value from 2 to 13; a value from 2 to 12; a value from 2 to 11; a value from 2 to 10; a value from 2 to 9; a value from 2 to 8; a value from 2 to 7; a value from 2 to 6; or a value of 2, 3, or 4.

[0345] Aspect 31. The thermoplastic copolyester elastomer composition as described in aspect 29, wherein the second copolyester unit has a structure represented by formula 6:

[0346]

[0347] Aspect 32. The thermoplastic copolyester elastomer composition of any one of Aspects 22-31, wherein the thermoplastic copolyester elastomer comprises, based on the total weight of the thermoplastic copolyester elastomer, about 30% to about 80% by weight; about 40% to about 80% by weight; about 50% to about 80% by weight; about 30% to about 70% by weight; about 40% to about 70% by weight; or about 50% to about 70% by weight of the more than one first copolyester unit.

[0348] Aspect 33. The thermoplastic copolyester elastomer composition of any one of Aspects 22-32, wherein the thermoplastic copolyester elastomer comprises about 40% to about 65% by weight based on the total weight of the thermoplastic copolyester elastomer; about 45% to about 65% by weight; about 50% to about 65% by weight; about 55% to about 65% by weight; about 40% to about 60% by weight; about 45% to about 60% by weight; about 50% to about 60% by weight; or about 55% to about 60% by weight of the more than one second copolyester unit.

[0349] Aspect 34. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-33, wherein the thermoplastic copolyester elastomer composition further comprises additives.

[0350] Aspect 35. The thermoplastic copolyester elastomer composition as described in aspect 34, wherein the additive is present in an amount from about 0.1% by weight to about 10% by weight based on the total weight of the foamed polymer material.

[0351] Aspect 36. The thermoplastic copolyester elastomer composition as described in aspect 34 or 35, wherein the additive is a wax, an antioxidant, a UV absorber, a colorant, or a combination thereof.

[0352] Aspect 37. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-36, wherein the thermoplastic copolyester elastomer composition further comprises filler.

[0353] Aspect 38. The thermoplastic copolyester elastomer composition as described in aspect 37, wherein the filler is present in an amount from about 0.05% by weight to about 20% by weight or from about 0.1% by weight to about 10% by weight based on the total weight of the foamed polymer material.

[0354] Aspect 39. The thermoplastic copolyester elastomer composition as described in any one of Aspects 37 or 38, wherein the filler is a particulate filler; or wherein the filler is a carbonaceous filler.

[0355] Aspect 40. The thermoplastic copolyester elastomer composition of aspect 39, wherein the carbonaceous filler is carbon black, activated carbon, graphite, carbon fiber, carbon fibrils, carbon nanoparticles or combinations thereof; and wherein the carbonaceous filler is optionally chemically modified.

[0356] Aspect 41. The thermoplastic copolyester elastomer composition as described in aspect 37, wherein the filler is an inorganic filler.

[0357] Aspect 42. The thermoplastic copolyester elastomer composition of aspect 41, wherein the inorganic filler is an oxide, hydroxide, salt, silicate, metal or a combination thereof; or wherein the inorganic filler comprises glass beads, glass fibers, hollow glass spheres, glass sheets, MgO, SiO2, Sb2O3, Al2O3, ZnO, talc, mica, kaolin, wollastonite or a combination thereof.

[0358] Aspect 43. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-42, wherein the thermoplastic copolyester elastomer composition is substantially composed of one or more thermoplastic copolyester elastomers.

[0359] Aspect 44. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-42 further comprises at least one ionomer.

[0360] Aspect 45. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-42 further comprises at least one thermoplastic polyurethane.

[0361] Aspect 46. The thermoplastic copolyester elastomer composition of any one of Aspects 1-45, wherein the thermoplastic copolyester elastomer composition is substantially free of thermoplastic polyamide polymers, including polyamide copolymers such as polyether block amide copolymers.

[0362] Aspect 47. The thermoplastic copolyester elastomer composition of any one of Aspects 1-45, wherein the thermoplastic copolyester elastomer composition is substantially free of thermoplastic polyolefin polymers, including polyethylene and polypropylene and / or polyolefin copolymers such as ethylene-vinyl acetate copolymers.

[0363] Aspect 48. The thermoplastic copolyester elastomer composition of any one of Aspects 1-47, wherein, when determined using a cyclic tensile test as described herein, the thermoplastic copolyester elastomer has a maximum load of about 10 N to about 100 N; about 15 N to about 50 N; or about 20 N to about 40 N.

[0364] Aspect 49. The thermoplastic copolyester elastomer composition of any one of Aspects 1-48, wherein the thermoplastic copolyester elastomer has an energy efficiency of more than or equal to about 50%; more than or equal to about 60%; or more than or equal to about 70% when determined using a cyclic tensile test as described herein.

[0365] Aspect 50. The thermoplastic copolyester elastomer composition of any one of Aspects 1-49, wherein, when determined using a cyclic tensile test as described herein, the thermoplastic copolyester elastomer has an energy return of about 1 J to 15 J; about 2 J to 12 J; or about 4 J to 10 J.

[0366] Aspect 51. The thermoplastic copolyester elastomer composition as described in any one of Aspects 1-50, wherein the thermoplastic copolyester elastomer has a tensile modulus of about 1 MPa to 15 MPa when determined using a cyclic tensile test as described herein.

[0367] Aspect 52. The thermoplastic copolyester elastomer composition of any one of Aspects 1-51, wherein, when determined using a cyclic tensile test as described herein, the thermoplastic copolyester elastomer has a zero shear viscosity of about 10 Pascal-second to about 10,000 Pascal-second; about 100 Pascal-second to about 7,000 Pascal-second; or about 1,000 Pascal-second to about 5,000 Pascal-second.

[0368] Aspect 53. A foam article comprising a foamed polymeric material, said foamed polymeric material comprising a thermoplastic copolyester elastomer composition as described in any one of Aspects 1-52; wherein said foam article has a porous foam structure.

[0369] Aspect 54. The foam article as described in aspect 53, wherein the foam article is an extruded foam article.

[0370] Aspect 55. The foam article as described in aspect 53, wherein the foam article is a compression-molded foam article.

[0371] Aspect 56. The foam article as described in any one of Aspects 53-55, wherein the foam article has a viscosity of about 1.0 kg / cm to 4.5 kg / cm, about 1.6 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 3.5 kg / cm, about 2.5 kg / cm to 3.5 kg / cm, or about 0.07 kg / cm to 2.0 kg / cm. The tear values ​​are approximately 0.8 kg / cm to 1.5 kg / cm, or approximately 0.9 kg / cm to 1.2 kg / cm, or approximately 1.5 kg / cm to 2.2 kg / cm; approximately 0.08 kg / cm to 4.0 kg / cm, approximately 0.9 kg / cm to 3.0 kg / cm, approximately 1.0 kg / cm to 2.0 kg / cm, approximately 1.0 kg / cm to 1.5 kg / cm, or approximately 2 kg / cm.

[0372] Aspect 57. A foam article as described in any one of Aspects 53-56, wherein the foam article has a tensile strength of from 5 kg / cm² to 25 kg / cm², or from 10 kg / cm² to 23 kg / cm², or from 15 kg / cm² to 22 kg / cm².

[0373] Aspect 58. The foam article of any one of Aspects 53-57, wherein the foam article has about 60% to 90%; about 60% to 85%; about 65% to 85%; about 70% to 85%; about 60% to 85%; about 65% to 80%; about 65% to 75%; about 70% to 80%; or about 75% to 80%; about 75% to 85%; about 80% to 95%; or about 85% to 95% of energy return.

[0374] Aspect 59. The foam article as described in any one of Aspects 53-58, wherein the foam article has a density of less than or equal to about 0.7 g per cubic centimeter; about 0.1 g per cubic centimeter to about 0.35 g per cubic centimeter; about 0.15 g per cubic centimeter to about 0.35 g per cubic centimeter; about 0.2 g per cubic centimeter to about 0.35 g per cubic centimeter; or about 0.1 g per cubic centimeter to about 0.22 g per cubic centimeter.

[0375] Aspect 60. The foam article of any one of Aspects 53-59, wherein the foam article has a specific gravity of from about 0.02 to about 0.22; from about 0.03 to about 0.12; from about 0.04 to about 0.10; from about 0.11 to about 0.12; from about 0.10 to about 0.12; from about 0.15 to about 0.2; from 0.15 to about 0.30; from 0.01 to about 0.10; from about 0.02 to about 0.08; from about 0.03 to about 0.06; from 0.08 to about 0.15; from about 0.10 to about 0.12; from about 0.15 to about 0.2; or from about 0.10 to about 0.12.

[0376] Aspect 61. The foam article of any one of Aspects 53-59, wherein the foam article has a stiffness of about 30 N / mm to about 275 N / mm; about 40 N / mm to about 275 N / mm; about 40 N / mm to about 100 N / mm; or about 50 N / mm to about 85 N / mm.

[0377] Aspect 62. The foam article as described in any one of Aspects 53-61, wherein the porous foam structure is a closed-cell foam structure.

[0378] Aspect 63. The foam article as described in any one of Aspects 53-61, wherein the porous foam structure is an open-cell foam structure.

[0379] Aspect 64. The foam article as described in any one of Aspects 53-63, wherein the porous foam has an average pore size from about 50 micrometers to about 5 mm; from about 100 micrometers to about 1 mm; or from about 50 micrometers to about 1 mm.

[0380] Aspect 65. A foam article as described in any one of Aspects 53-63, wherein when measured on a foam board having a thickness of about 1 cm, the foam article has a displacement change of about 0.75 mm or less under a maximum load, wherein the foam board is compressed for about 5000 compression cycles, each cycle from 0 N to 300 N and back to 0 N, using a 45 mm diameter tube as a compression head.

[0381] Aspect 66. A foam article as described in any one of Aspects 53-63, wherein when measured on a foam board having a thickness of about 1 cm, the foam article has a displacement change of about 0.1 mm or less under a maximum load, wherein the foam board is compressed for about 5000 compression cycles, each cycle from 0 N to 300 N and back to 0 N, using a 45 mm diameter tube as the compression head.

[0382] Aspect 67. A method for manufacturing a foam article, the method comprising: forming a mixture of a molten polymer material and a foaming agent, the molten polymer material comprising a thermoplastic elastomer; injecting the mixture into a mold cavity; foaming the molten polymer material to form a foamed molten polymer material; solidifying the foamed molten polymer material to form a foam article having a microporous foam structure; and removing the foam article from the mold cavity.

[0383] Aspect 68. The method of aspect 67, wherein the thermoplastic elastomer is a thermoplastic copolyester elastomer as described in any one of aspects 1-52.

[0384] Aspect 69. The method as described in aspect 67 or aspect 68, wherein the foaming agent is a physical foaming agent.

[0385] Aspect 70. The method of aspect 69, wherein the physical foaming agent is a supercritical fluid.

[0386] Aspect 71. The method of aspect 70, wherein the supercritical fluid comprises nitrogen or a supercritical fluid thereof.

[0387] Aspect 72. The method of aspect 71, wherein the supercritical fluid comprises nitrogen or a supercritical fluid thereof or is substantially composed of nitrogen or a supercritical fluid thereof.

[0388] Aspect 73. The method of aspect 71, wherein the supercritical fluid further comprises carbon dioxide or a supercritical fluid thereof.

[0389] Aspect 74. The method of aspect 73, wherein the carbon dioxide is present in an amount of about 1% to about 3% or about 1% to about 5% by weight based on the total weight of the mixture.

[0390] Aspect 75. The method of any one of Aspects 71-74, wherein the nitrogen gas is present in an amount of about 1% to about 3% or about 1% to about 5% by weight based on the total weight of the mixture.

[0391] Aspect 76. The method of any one of Aspects 68-74, wherein forming the mixture of the molten polymer material and the physical foaming agent comprises adding the physical foaming agent to the molten polymer material and forming a single-phase solution of the physical foaming agent dissolved in the molten polymer material.

[0392] Aspect 77. The method of any one of Aspects 68-74, wherein forming the mixture of the molten polymer material and the physical foaming agent comprises injecting the physical foaming agent into a solid resin comprising the polymer material to form an injected resin, and melting the injected resin to form a single-phase solution of the physical foaming agent dissolved in the molten polymer mixture.

[0393] Aspect 78. The method of any one of Aspects 68-77, wherein injecting the mixture into the mold cavity comprises injecting the mixture into a pressurized mold cavity having a first pressure greater than atmospheric pressure; and foaming the molten polymer material comprises reducing the first pressure to a second pressure and initiating bubble formation by the physical foaming agent, thereby foaming the molten polymer material.

[0394] Aspect 79. The method of any one of Aspects 76-78, wherein injecting the mixture into the mold cavity comprises injecting the mixture into a pressurized mold cavity having a first pressure greater than atmospheric pressure.

[0395] Aspect 80. The method of aspect 79, wherein the method comprises applying a gas back pressure to the mold cavity from about 100 psi to about 3,000 psi, or from about 550 psi to about 1,500 psi, or from about 650 psi to about 1,000 psi, and wherein the gas back pressure is applied to the mold cavity prior to the foaming.

[0396] Aspect 81. The method of aspect 78, wherein the second pressure is atmospheric pressure; and wherein reducing the first pressure to the second pressure comprises venting the pressurized mold cavity to atmospheric pressure.

[0397] Aspect 82. The method of aspect 78, wherein the second pressure is atmospheric pressure; and wherein reducing the first pressure to the second pressure comprises using a controlled pressure reduction rate until the mold cavity has a pressure substantially equal to atmospheric pressure.

[0398] Aspect 83. The method of aspect 82, wherein the controlled pressure reduction rate is from about 10 psi per second to about 600 psi per second, or from about 15 psi per second to about 300 psi per second, or from about 20 psi per second to about 150 psi per second.

[0399] Aspect 84. The method of aspect 78, wherein the second pressure is atmospheric pressure; and wherein reducing the first pressure to the second pressure includes reducing the pressure in more than one step until the mold cavity has a pressure substantially equal to atmospheric pressure.

[0400] Aspect 85. The method of aspect 67, wherein the foaming agent is a chemical foaming agent.

[0401] Aspect 86. The method of aspect 85, wherein the chemical foaming agent is present in an amount from about 0.05% by weight to about 25% by weight or from about 0.1% by weight to about 10% by weight based on the total weight of the polymer mixture.

[0402] Aspect 87. The method as described in aspect 85 or aspect 86, wherein the chemical foaming agent is an azo compound.

[0403] Aspect 88. The method of any one of Aspects 67-87, wherein the foam article is substantially free of chemical foaming agents or their decomposition products.

[0404] Aspect 89. The method of any one of Aspects 67-87, wherein the foam article is substantially free of physical foaming agents.

[0405] Aspect 90. The method of any one of Aspects 67-89, wherein the mixture has an injection temperature; and wherein the injection temperature is from about the melting temperature of the thermoplastic elastomer to about 50°C above the tail temperature of the thermoplastic elastomer.

[0406] Aspect 91. The method of aspect 90, wherein the injection temperature is from about the melting temperature of the thermoplastic elastomer to a temperature about 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C above the tail temperature of the thermoplastic elastomer.

[0407] Aspect 92. The method of any one of Aspects 67-91, wherein the foaming occurs at a foaming temperature; and wherein the foaming temperature is from about the melting temperature of the thermoplastic elastomer to about 50°C above the tail temperature of the thermoplastic elastomer.

[0408] Aspect 93. The method of aspect 92, wherein the foaming temperature is a temperature ranging from approximately the melting temperature of the thermoplastic elastomer to approximately 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C above the tail temperature of the thermoplastic copolyester elastomer.

[0409] Aspect 94. The method of any one of Aspects 67-93, wherein the foam article is a thermoplastic foam article.

[0410] Aspect 95. The method of any one of Aspects 67-94, wherein the porous foam structure is a closed-cell foam structure.

[0411] Aspect 96. The method of any one of Aspects 67-94, wherein the porous foam structure is an open-cell foam structure.

[0412] Aspect 97. The method of any one of Aspects 67-96, wherein the porous foam has an average pore size from about 50 micrometers to about 5 mm; from about 100 micrometers to about 1 mm; or from about 50 micrometers to about 1 mm.

[0413] Aspect 98. The method of any one of Aspects 67-96, wherein the thermoplastic elastomer does not form crosslinks during foaming; or wherein the thermoplastic elastomer does not form crosslinks during curing.

[0414] Aspect 99. The method of any one of Aspects 67-98, wherein the curing comprises cooling the mold cavity; or wherein the curing comprises cooling the foamed molten polymer material.

[0415] Aspect 100. The method of any one of Aspects 67-99, wherein the foaming comprises releasing pressure from the mold cavity at a mold cavity pressure release rate.

[0416] Aspect 101. The method of aspect 100, wherein the mold cavity pressure release rate is about 10 psi per second to about 600 psi per second, or about 15 psi per second to about 300 psi per second, or about 20 psi per second to about 150 psi per second.

[0417] Aspect 102. The method of any one of Aspects 67-99, wherein the foaming comprises providing gas back pressure to the mold cavity.

[0418] Aspect 103. The method as described in aspect 102, wherein the gas back pressure is at least about 550 psi, about 550 psi to about 1500 psi, or about 650 psi to about 1000 psi.

[0419] Aspect 104. The method of aspect 103, wherein the foaming agent is a physical foaming agent; or wherein the foaming agent is supercritical nitrogen.

[0420] Aspect 105. The method of any one of Aspects 67-104, the method further comprising placing a textile element in the mold cavity prior to injecting the mixture, and foaming the molten polymer material in contact with the textile element.

[0421] Aspect 106. The method of aspect 105, wherein the textile element comprises thermoplastic polyester fiber, thermoplastic polyester yarn, thermoplastic polyurethane fiber, thermoplastic polyurethane yarn, thermoplastic polyamide fiber, thermoplastic polyamide yarn, or a combination thereof.

[0422] Aspect 107. The method as described in aspect 105 or aspect 106, wherein the textile element is a component for the upper of a footwear article.

[0423] Aspect 108. The method of any one of Aspects 67-107, wherein the foam article is a component of a footwear article.

[0424] Aspect 109. The method of any one of aspects 67-107, wherein the foam article is a component of a clothing article.

[0425] Aspect 110. The method of any one of Aspects 67-107, wherein the foam article is a component of a sports equipment article.

[0426] Aspect 111. The method of any one of Aspects 67-110, wherein the thermoplastic copolyester elastomer has a maximum load of about 10 N to about 100 N when determined using a cyclic tensile test as described herein.

[0427] Aspect 112. The method of aspect 111, wherein the thermoplastic copolyester elastomer has a maximum load of about 15 N to about 50 N when determined using a cyclic tensile test as described herein.

[0428] Aspect 113. The method of aspect 111, wherein the thermoplastic copolyester elastomer has a maximum load of about 20 N to about 40 N when determined using a cyclic tensile test as described herein.

[0429] Aspect 114. The method of any one of Aspects 67-113, wherein the thermoplastic copolyester elastomer has an energy efficiency of more than or equal to about 50%; more than or equal to about 60%; or more than or equal to about 70% when determined using a cyclic tensile test as described herein.

[0430] Aspect 115. The method of any one of Aspects 67-114, wherein when determined using a cyclic tensile test as described herein, the thermoplastic copolyester elastomer has an energy return of about 1 J to about 15 J; about 2 J to about 12 J; or about 4 J to 10 J.

[0431] Aspect 116. The method of any one of Aspects 67-115, wherein the thermoplastic copolyester elastomer has a tensile modulus of about 1 MPa to 15 MPa when determined using a cyclic tensile test as described herein.

[0432] Aspect 117. The method of any one of Aspects 67-116, wherein the thermoplastic copolyester elastomer has a zero shear viscosity of about 10 Pascal-second to about 10,000 Pascal-second; about 100 Pascal-second to about 7,000 Pascal-second; or about 1,000 Pascal-second to about 5,000 Pascal-second when determined using a cyclic tensile test as described herein.

[0433] Aspect 118. The method of any one of Aspects 67-117, wherein when determined using a cyclic tensile test as described herein, the foam article has a tensile test value greater than or equal to about 30 kg / cm.

[0434] Aspect 119. The method of any one of Aspects 67-118, wherein when determined using a cyclic tensile test as described herein, the foam article has a plyometric tear test value greater than or equal to about 1.5 kg / cm.

[0435] Aspect 120. The method of any one of Aspects 67-119, wherein the foam article has a density of less than or equal to about 0.7 g / cm³; about 0.1 g / cm³ to about 0.35 g / cm³; about 0.15 g / cm³ to about 0.35 g / cm³; about 0.2 g / cm³ to about 0.35 g / cm³; or about 0.1 g / cm³ to about 0.22 g / cm³.

[0436] Aspect 121. The method of any one of Aspects 67-120, wherein the foam article has a stiffness of about 30 N / mm to about 275 N / mm; about 40 N / mm to about 275 N / mm; about 40 N / mm to about 100 N / mm; or about 50 N / mm to about 85 N / mm.

[0437] Aspect 122. The method of any one of Aspects 67-121, wherein when a foam board having a thickness of about 1 cm is measured, the foam article has a displacement change of about 0.75 mm or less under a maximum load, wherein the foam board is compressed for about 5000 compression cycles, each cycle from 0 N to 300 N and back to 0 N, using a 45 mm diameter tube as the compression head.

[0438] Aspect 123. The method of any one of Aspects 67-121, wherein when a foam board having a thickness of about 1 cm is measured, the foam article has a displacement change of about 0.1 mm or less under a maximum load, wherein the foam board is compressed for about 5,000 compression cycles, each cycle from 0 N to 300 N and back to 0 N, using a 45 mm diameter tube as the compression head.

[0439] Aspect 124. The method of any one of Aspects 67-123, wherein the injection includes monitoring the injection pressure of the mixture before or during the injection, and controlling the injection based on the injection pressure of the mixture.

[0440] Aspect 125. The method of any one of Aspects 67-123, wherein the injection includes controlling the injection temperature of the mixture before the mixture enters the mold cavity.

[0441] Aspect 126. The method of any one of Aspects 67-123, wherein the injection includes controlling the temperature of the mold cavity before the mixture enters the mold cavity.

[0442] Aspect 127. The method of any one of Aspects 67-126, wherein the mixture has an expansion ratio of 1 relative to the volume of the mold cavity.

[0443] Aspect 128. The method of any one of Aspects 67-126, wherein after the foam article is removed from the mold cavity, the foam article is cooled to about 25°C and the foam article is balanced at about 25°C and a pressure of about 1 atm, the volume of the balanced foam article being within plus or minus 5 percent of the volume of the mold cavity.

[0444] Aspect 129. An article comprising a foam article as described in any one of Aspects 53-66 or a foam article manufactured by any one of Aspects 67-128.

[0445] Aspect 130. The article as described in aspect 129, wherein the article is a footwear article.

[0446] Aspect 131. The article as described in aspect 130, wherein the foam article is a cushioning element in the footwear article.

[0447] Aspect 132. The article as described in aspect 131, wherein the cushioning element is a component of the sole structure in the footwear article.

[0448] Aspect 133. The article as described in aspect 132, wherein the sole structure further includes the outsole component on the ground-facing side of the outsole component.

[0449] Aspect 134. The article as described in aspect 133, wherein the outsole component comprises cured rubber.

[0450] Aspect 135. The article as described in any one of Aspects 129-134, wherein the article includes the side of the foam article bonded to the upper.

[0451] Aspect 136. The article as described in aspect 135, wherein the upper comprises thermoplastic polyester yarn, thermoplastic polyester fiber, thermoplastic polyurethane yarn, thermoplastic polyurethane fiber, thermoplastic polyamide yarn, thermoplastic polyamide fiber, or a combination thereof.

[0452] Aspect 137. The article as described in aspect 135 or aspect 136, wherein the sides of the foam article bonded to the shoe upper are bonded using an adhesive.

[0453] Aspect 138. The article as described in aspect 135 or aspect 136, wherein the side of the foam article bonded to the shoe upper is substantially free of adhesive at the bonding interface between the side of the foam article and the shoe upper.

[0454] Aspect 139. The article as described in aspect 129, wherein the article is a clothing article.

[0455] Aspect 140. The article as described in aspect 129, wherein the article is a sports equipment article.

[0456] Aspect 141. A method for manufacturing footwear articles, the method comprising: attaching a foam article and a textile element to each other; wherein the foam article is a foam article as described in any one of Aspects 53-66; or wherein the foam article is a foam article manufactured by any one of Aspects 67-128.

[0457] Aspect 142. A method for manufacturing footwear articles, the method comprising: attaching an outsole to a sole interlayer; wherein the outsole comprises an outsole thermoplastic copolyester elastomer; and wherein the sole interlayer comprises a foam article as described in any one of Aspects 53-66, or a foam article manufactured by any one of Aspects 67-128.

[0458] Aspect 143. The method of aspect 142, wherein the thermoplastic copolyester elastomer of the outsole comprises the thermoplastic copolyester elastomer as described in any one of aspects 1-52.

[0459] Aspect 144. The method of aspect 142, wherein the thermoplastic copolyester elastomer of the outsole is substantially free of the thermoplastic copolyester elastomer as described in any one of aspects 1-52.

[0460] Aspect 145. The method of any one of Aspects 142-144, wherein the outsole is substantially free of foamed thermoplastic copolyester elastomer.

[0461] Aspect 146. The method of any one of Aspects 142-144, wherein the outsole comprises a foamed thermoplastic copolyester elastomer.

[0462] Aspect 147. The method of any one of Aspects 142-146, wherein the midsole comprises a midsole foamed thermoplastic copolyester composition, the midsole foamed thermoplastic copolyester composition comprising a first polymer component containing at least one first thermoplastic copolyester; and the outsole comprises an outsole thermoplastic copolyester composition, the outsole thermoplastic copolyester composition comprising a second polymer component containing at least one second thermoplastic copolyester; and wherein the concentration of the additive in the foamed thermoplastic copolyester composition differs from the concentration of the additive in the outsole thermoplastic copolyester composition by at least 10 weight percentages, or the first concentration of the first polymer component in the foamed thermoplastic copolyester composition differs from the second concentration of the second polymer component in the outsole thermoplastic copolyester composition by at least 10 weight percentages, or the chemical structure of the at least one first thermoplastic copolyester differs from the chemical structure of the at least one second thermoplastic copolyester, or the number average molecular weight of the at least one first thermoplastic copolyester differs from the number average molecular weight of the at least one second thermoplastic copolyester by at least 10 percentage points, or any combination thereof.

[0463] Aspect 148. The method of any one of Aspects 142-147, wherein the attachment comprises injection molding the outsole and then directly injection molding the outsole interlayer onto the outsole.

[0464] Aspect 149. The method of any one of Aspects 142-147, wherein the attachment comprises thermally bonding the sole interlayer to the outsole.

[0465] Aspect 150. A molding system for forming a foam article, the system comprising: a barrel housing a screw, the barrel being configured to receive molten polymer material and form a mixture comprising a thermoplastic elastomer and a foaming agent, and configured to adjust the position of the screw within the barrel to adjust the flow rate of the mixture out of the barrel; a mold cavity configured to contain the mixture during foaming, mold the foamed mixture, and solidify the molded foamed mixture onto the foam article; an injection or extrusion device configured to receive the mixture and extrude or inject it into the mold cavity at an injection pressure and an injection temperature; and a temperature control and monitoring system configured to control an injection temperature or a foaming temperature, wherein the molten polymer material foams within the mold cavity at the injection temperature or the foaming temperature, or both.

[0466] Aspect 151. The molding system of aspect 150, wherein the temperature control and monitoring system is configured to control the injection temperature of the mixture or the foaming temperature of the molten polymer material, or both, within a temperature range from approximately the melting temperature of the thermoplastic elastomer to approximately 50°C above the tail temperature of the thermoplastic elastomer.

[0467] Aspect 152. The molding system as described in aspect 150 or aspect 151 further includes a gas backpressure assembly coupled to the mold cavity, wherein the gas backpressure assembly is configured to regulate the amount of backpressure gas flowing into the mold cavity before, during, or after the mixture is extruded or injected into the mold cavity or during the foaming of the molten polymer material in the mold cavity.

[0468] Aspect 153. The molding system of any one of Aspects 150-152 further includes a mold cavity venting system configured to regulate the rate of pressure loss due to gas flowing out of the mold cavity.

[0469] Aspect 154. The molding system as described in any one of Aspects 150-153, wherein the system further comprises a flow channel system in fluid communication with the injection or extrusion device and the mold cavity.

[0470] Aspect 155. The molding system of aspect 154, wherein the runner system is configured to control the temperature of the mixture as the mixture flows through the runner.

[0471] Aspect 156. The molding system of aspect 155, wherein the runner system is configured to heat the mixture as it flows through the runner.

[0472] Aspect 157. The molding system of any one of Aspects 150-156, wherein the system includes a pressure control component configured to control the pressure of the mixture when the mixture enters the mold cavity.

[0473] Aspect 158. A method for operating a molding system for forming a foam article, the method comprising: forming a mixture of a molten polymer material comprising a thermoplastic elastomer and a foaming agent in a barrel housing a screw; adjusting the position of the screw in the barrel to adjust the flow rate of the mixture out of the barrel; allowing the mixture to flow from the barrel into a mold cavity; extruding or injecting the mixture into the mold cavity at an injection pressure and an injection temperature; foaming the molten polymer material in the mold cavity at a foaming temperature to form a foamed molten polymer material; and solidifying the foamed molten polymer material in the mold cavity to form a foam article having a porous foam structure.

[0474] Aspect 159. The method of operation as described in aspect 158, wherein the method further comprises monitoring and controlling the injection temperature of the mixture or the foaming temperature of the molten polymer material, or both, within a temperature range from approximately the melting temperature of the thermoplastic elastomer to approximately 50°C above the tail temperature of the thermoplastic elastomer.

[0475] Aspect 160. The method of operation as described in aspect 158 ​​or aspect 159 further includes adjusting the amount of back pressure gas flowing into the mold cavity before, during, or after the mixture is extruded or injected into the mold cavity, or during the foaming of the molten polymer material in the mold cavity.

[0476] Aspect 161. The method of operation as described in any one of Aspects 158-160, further comprising releasing gas from the mold cavity at a controlled rate during the extrusion or injection or during the foaming process.

[0477] Aspect 162. The method of operation as described in any one of Aspects 158-161, further comprising controlling the temperature of the mixture as the mixture flows through the flow channel into the mold cavity.

[0478] Aspect 163. The method of operation as described in any one of Aspects 158-162, further comprising controlling the injection pressure of the mixture when the mixture enters the mold cavity.

[0479] Aspect 164. The method of operation as described in any one of Aspects 158-163, wherein the molten polymer material comprises a thermoplastic copolyester elastomer according to any one of Aspects 1-52, or the foam article comprises a foam article according to any one of Aspects 53-66, or the method is a method of manufacturing a foam article according to any one of Aspects 67-128, or any combination thereof.

[0480] As will be seen from the foregoing, the aspects of this paper are well suited to achieving all the goals and objectives stated above, as well as other advantages that are evident and inherent to the structure.

[0481] Although specific elements and steps are discussed in combination, it should be understood that any element and / or step provided herein is intended to be combined with any other element and / or step, whether expressly stated or not, and remains within the scope provided herein.

[0482] It will be understood that certain features and sub-combinations are practical and can be employed without reference to other features and sub-combinations. This is contemplated by and within the scope of the claims.

[0483] Since many possible aspects can be made without departing from the scope of this document, it should be understood that everything stated herein or shown in the figures and detailed descriptions should be interpreted illustratively and not in a restrictive sense.

[0484] It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Those skilled in the art will recognize many variations and modifications to the aspects described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0485] Having described aspects of this disclosure, the following embodiments illustrate some additional aspects of this disclosure. While aspects of this disclosure have been described in conjunction with the following embodiments and the corresponding text and drawings, it is not intended to limit the aspects of this disclosure to this description. Rather, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of this disclosure. Example

[0486] Having described aspects of this disclosure, the following embodiments illustrate some additional aspects of this disclosure. While aspects of this disclosure have been described in conjunction with the following embodiments and the corresponding text and drawings, it is not intended to limit the aspects of this disclosure to this description. Rather, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of this disclosure.

[0487] Material.

[0488] 3078 and 4068 was obtained from DuPont (Wilmington, Delaware, USA); Pelprene TM The P-30B was obtained from Toyobo USA Inc. (New York, New York, USA); and 5400 was obtained from Samyang Corporation (Korea).

[0489] Characterization of solid polymers.

[0490] Dynamic scanning calorimetry (DSC) was performed on a TA Instruments Q2000. 10-30 mg of undried resin pellets were cycled from -90°C to 225°C at 20°C / min and cooled to -90°C at 10°C / min. In some cases, experiments were run using heat-cold-heat curves at heating / cooling rates of 10°C / min, with a minimum temperature of 0°C and a maximum temperature of 250°C. Two runs were performed for each material. T0 was recorded from the second cycle. m Value and T g The melt "peak" is determined as the local maximum value of the second heating cycle. If more than one peak exists in the DSC curve, the peak occurring at the hotter temperature is selected as the molding temperature reference. The tail is determined as the intersection of the tangent to the line on the higher temperature side of the melt peak and the extrapolated baseline. A schematic diagram of the method used to determine the peak temperature and tail temperature is illustrated in [the diagram]. Figure 7 As shown in the image.

[0491] Dynamic mechanical analysis (DMA) was performed on a TA Instruments Q800 (New Castle, Delaware, USA). Solid 150mm × 100mm × 2mm (L × W × H) substrates for each material were injection molded. Samples of approximately 10mm × 60mm × 2mm (L × W × H) were punched from the injection-molded substrates. Strain scanning and frequency scanning experiments were run at 25°C. Strain scanning experiments were performed at 1Hz from 2 × 10⁻⁶ Hz. -4 Sampling was performed within the range of 1% to 2% strain. For frequency sweep experiments with 0.1% strain, sampling was conducted at 10 points per decibel from 0.5 Hz to 100 Hz. Temperature sweep experiments were performed at 1 Hz with 0.1% strain, at a rate of 5 °C / min from -20 °C to 100 °C. Glass transition temperature T gRecord the peak value of the loss modulus G″. If G″ has no peak value, then the peak value of tanδ is recorded as T. g Record the values ​​of G′, G″, and tanδ at 25℃.

[0492] Viscosity measurements were collected using a flat parallel plate on a TA Instruments DHR-3 rheometer. Circular samples with a 25 mm cross-section and approximately 2 mm thickness were punched from a solid injection-molded substrate. Samples were dried before being placed in the rheometer. All samples were equilibrated at 180°C for 2–5 minutes and trimmed to obtain a final gap of <1 mm. Shear rates were measured from 0.01 s⁻¹. -1 up to 100s -1 Flow scanning experiments were conducted. Data were fitted to the Carreau, Carreau-Yasuda, and Williamson models, and the best fit was selected to record the zero-shear viscosity value. Polymer melt flow profiles were determined at temperatures, for example, 20°C above the melting point as determined by DSC as described above.

[0493] Cyclic tensile testing can be performed on dog-bone shaped specimens with a thickness of 2 mm. During testing, the specimens can be placed under a preload of 0 N–20 N. In some cases, the preload is 5 N. Strain is controlled to extend the range of 1%–25% of the extension. In some cases, the strain is controlled to extend to 6% of the extension. Cyclic tensile testing is used to determine the average stiffness, creep, maximum strain (“Max Strain”), and efficiency in the data shown below.

[0494] Characterization of foam polymers.

[0495] The specific gravity (SG) of 10mm-20mm foam substrates was measured using a Densicom Tester (Qualitest, Plantation, Florida, USA). The pre-weighed sample was immersed in a water bath, and the specific gravity was calculated using the ratio of the sample's mass in air to its mass in water.

[0496] Water absorption. The foamed sample was dried in a vacuum oven at 50°C for 2 days, followed by immersion in a water bath for 24 hours. Surface water was removed by gently blotting the surface of the sample before weighing. Water absorption was calculated as the percentage mass difference between the dry and wet samples.

[0497] The force / displacement behavior of foams and foamed articles was measured using an Instron Electropuls E10000 (Instron, Norwood, Massachusetts, USA) with a stainless steel 45mm circular cross-section impact geometry. Most foam sheets were approximately 10mm thick, with some thinner or thicker. Each sample was evaluated through two different compression cycles: a “run” and a “walk”. The “run” compression cycle consisted of the sample being compressed from 0N to 300N and back to 0N within 180ms under displacement control, followed by a 400ms pause, for a total of ~1.7Hz. The “walk” compression cycle consisted of the sample being compressed from 0N to 144N and back to 0N within 600ms, followed by a 400ms pause, for a total of ~1Hz. The corresponding force-displacement data provide information on foam modulus (stiffness), hysteresis (energy efficiency), deformation, fatigue behavior, etc., after many cycles. A typical characterization run using the compression sequence described above is performed for 5,000 cycles, simulating approximately 5-10 miles of walking / running and taking about 45 minutes of testing time on Electropuls. Longer runs of up to 100,000 compression cycles are performed to simulate the accelerated material response at approximately 100-200 miles.

[0498] Energy input is considered as the integral of the force-displacement curve during compressive loading. Energy output is considered as the integral of the force-displacement curve during unloading. Hysteresis is considered as a ratio: (energy output) / (energy input), which can also be considered as the energy efficiency of the foam. Fatigue behavior is determined by the change in foam displacement under the maximum load of the cycle. Thousands of cycles were performed on both running and walking compression cycles, measuring all properties: stiffness, hysteresis, and fatigue.

[0499] Processing conditions.

[0500] The foam substrate is prepared according to the conditions shown in Table 1 below.

[0501] Table 1.

[0502]

[0503] Prepare the foam shoe sole interlayer according to the conditions shown in Table 2 below.

[0504] Table 2.

[0505]

[0506] The foam substrate is prepared according to the conditions shown in Table 3 below.

[0507] Table 3.

[0508]

[0509] The cross-sectional view of the foam substrate described above is in Figures 8A-8D (Regarding numbers 2-5 above) and Figure 9 (As shown in number 1 above).

[0510] Exemplary data for foam substrates.

[0511] As described above 4068 is used to prepare the foam substrate. Exemplary compressed data is available in... Figure 6 As shown in the figure. The data was obtained by performing a cyclic compression test on a substrate in the form of a cylindrical tube with the following dimensions: thickness - 20 mm; diameter - 44.86 mm. Figure 6 The compressed data in the table are representative compression curves. The data obtained from these tests are summarized in Table 4 below.

[0512] Table 4.*

[0513]

[0514] *“Average modulus” is “average tensile modulus”.

[0515] The specific gravity of the foam substrate prepared as described above was determined to be for... 4068 is 0.16-0.28 and for 3078 is 0.17-0.26.

[0516] As described above, the specific gravity of the prepared foam shoe sole interlayer was determined to be for... 4068 is 0.19-0.27 and for 3078 is 0.19-0.26.

[0517] The foam substrates described in Table 3 above were subjected to energy return analysis as described herein. The results are shown in Table 5 below.

[0518] Table 5.

[0519]

[0520] It should be emphasized that the aspects described above in this disclosure are merely possible examples of implementation methods and are only presented for the purpose of clearly understanding the principles of this disclosure. Many variations and modifications can be made to the aspects described above without substantially departing from the spirit and principles of this disclosure. All such modifications and variations are intended to be included within the scope of this disclosure.

Claims

1. A sole interlayer for footwear articles, the sole interlayer comprising a thermoplastic foam article, the thermoplastic foam article comprising: A foamed polymer material having an open-cell porous foam structure and a specific gravity from 0.02 to 0.30, the foamed polymer material comprising a thermoplastic copolyester elastomer, wherein the thermoplastic copolyester elastomer comprises: (a) More than one first segment, each first segment being derived from a dihydroxy-terminated polydiol; (b) More than one second segment, each of which is derived from a diol; as well as (c) More than one third segment, each third segment derived from an aromatic dicarboxylic acid; and The more than one first segment, the more than one second segment, and the more than one third segment are arranged such that the thermoplastic copolyester elastomer comprises: More than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polyethylene glycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1: (1) R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of 400 to 6000; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment. as well as More than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2: (2) Wherein R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

2. The sole interlayer according to claim 1, wherein the first copolyester unit has a structure represented by formula 3: (3)， Wherein R is H or methyl; where y is an integer having a value from 1 to 10; where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from 300 Daltons to 7,000 Daltons.

3. The sole interlayer according to claim 2, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

4. The sole interlayer according to claim 2, wherein y is an integer having a value of 1, 2 or 3.

5. The shoe sole interlayer according to claim 2, wherein R is hydrogen.

6. The shoe sole interlayer according to claim 2, wherein R is methyl.

7. The sole interlayer according to claim 2, wherein R is hydrogen, and y is an integer having a value of 1, 2, or 3.

8. The sole interlayer according to claim 2, wherein R is methyl and y is an integer having a value of 1.

9. The sole interlayer according to claim 1, wherein the first copolyester unit has a structure represented by Formula 4: (4)， Where z is an integer having a value from 2 to 60; and the weight-average molecular weight of each of the more than one first copolyester unit is from 300 Daltons to 7,000 Daltons.

10. The sole interlayer according to claim 9, wherein z is an integer having a value from 5 to 60.

11. The sole interlayer of claim 9, wherein the weight-average molecular weight of each of the more than one first copolyester unit is from 400 Daltons to 6,000 Daltons.

12. The sole interlayer according to claim 1, wherein the second copolyester unit has a structure represented by Formula 5: (5)， Where x is an integer with values ​​from 1 to 20.

13. The sole interlayer of claim 12, wherein x is an integer having a value from 2 to 18.

14. The midsole of claim 1, wherein the thermoplastic copolyester elastomer comprises 30 to 80% by weight of the more than one first copolyester unit based on the total weight of the thermoplastic copolyester elastomer.

15. The midsole of claim 1, wherein the thermoplastic copolyester elastomer comprises the more than one second copolyester unit comprising 40 to 65% by weight of the total weight of the thermoplastic copolyester elastomer.

16. The sole interlayer of claim 1, wherein the thermoplastic foam article has a specific gravity from 0.02 to 0.

22.

17. The midsole of claim 1, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of 50,000 Daltons to 1,000,000 Daltons.

18. The midsole of claim 1, wherein the thermoplastic copolyester elastomer has a ratio of the first segment to the third segment of 1:1 to 1:5 based on the weight of each of the first segment and the third segment; or wherein the thermoplastic copolyester elastomer has a ratio of the second segment to the third segment of 1:1 to 1:3 based on the weight of each of the second segment and the third segment.

19. A method for injection molding a thermoplastic foam article, said thermoplastic foam article comprising a porous foam structure having open cells and a foamed polymer material with a specific gravity from 0.02 to 0.30, wherein said method comprises: A mixture of a molten polymer material and a foaming agent is formed, wherein the molten polymer material comprises a thermoplastic copolyester elastomer; The mixture is injected into the mold cavity; The molten polymer material is foamed to form a foamed molten polymer material; The foamed molten polymer material is solidified to form a foam article with a porous foam structure; and Remove the thermoplastic foam article from the mold cavity; The thermoplastic copolyester elastomer comprises: (a) More than one first segment, each first segment being derived from a dihydroxy-terminated polydiol; (b) More than one second segment, each of which is derived from a diol; as well as (c) More than one third segment, each third segment derived from an aromatic dicarboxylic acid; and The more than one first segment, the more than one second segment, and the more than one third segment are arranged such that the thermoplastic copolyester elastomer comprises: More than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polyethylene glycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1: (1) R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of 400 to 6000; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment. as well as More than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2: (2) Wherein R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

20. The method of claim 19, wherein the first copolyester unit has a structure represented by formula 3: (3)， Wherein R is H or methyl; where y is an integer having a value from 1 to 10; where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester unit is from 300 Daltons to 7,000 Daltons.

21. The method of claim 20, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

22. The method of claim 20, wherein y is an integer having a value of 1, 2 or 3.

23. The method of claim 20, wherein R is hydrogen.

24. The method of claim 20, wherein R is methyl.

25. The method of claim 20, wherein R is hydrogen and y is an integer having a value of 1, 2 or 3.

26. The method of claim 20, wherein R is a methyl group and y is an integer having a value of 1.

27. The method of claim 19, wherein the first copolyester unit has a structure represented by Formula 4: (4)， Where z is an integer having a value from 2 to 60; and the weight-average molecular weight of each of the more than one first copolyester unit is from 300 Daltons to 7,000 Daltons.

28. The method of claim 27, wherein z is an integer having a value from 5 to 60.

29. The method of claim 27, wherein the weight-average molecular weight of each of the more than one first copolyester unit is from 400 Daltons to 6,000 Daltons.

30. The method of claim 19, wherein the second copolyester unit has a structure represented by formula 5: (5)， Where x is an integer with values ​​from 1 to 20.

31. The method of claim 30, wherein x is an integer having a value from 2 to 18.

32. The method of claim 19, wherein the thermoplastic copolyester elastomer comprises 30 to 80% by weight of the more than one first copolyester unit based on the total weight of the thermoplastic copolyester elastomer.

33. The method of claim 19, wherein the thermoplastic copolyester elastomer comprises 40 to 65% by weight of the more than one second copolyester unit based on the total weight of the thermoplastic copolyester elastomer.

34. The method of claim 19, wherein the thermoplastic foam article has a specific gravity from 0.02 to 0.

22.

35. The method of claim 19, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of 50,000 Daltons to 1,000,000 Daltons.

36. The method of claim 19, wherein the thermoplastic copolyester elastomer has a ratio of the first segment to the third segment of 1:1 to 1:5 based on the weight of each of the first segment and the third segment; or wherein the thermoplastic copolyester elastomer has a ratio of the second segment to the third segment of 1:1 to 1:3 based on the weight of each of the second segment and the third segment.

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