阅读说明：本技术 注塑前体的发泡方法 (Foaming process for injection molding precursors ) 是由 布莱恩·N·法里斯 大卫·特纳 于 2016-10-27 设计创作，主要内容包括：本申请涉及一种注塑前体的发泡方法。一种制造发泡制品的方法,包括：(a)注塑熔融的热塑性弹性体以形成前体；(b)使该热塑性弹性体交联；(c)将热塑性弹性体加热至第一温度以软化该热塑性弹性体；(d)在第一压力下用至少一种惰性气体对该热塑性弹性体进行输注,第一压力足以使得该至少一种惰性气体渗透到软化的热塑性弹性体中；以及(e)在制品软化的同时,将压力减至低于所述第一压力的第二压力,以使前体至少部分发泡成发泡制品,其中发泡制品与前体的形状基本相同。(The present application relates to a method of foaming an injection molded precursor. A method of making a foamed article comprising: (a) injection molding the molten thermoplastic elastomer to form a precursor; (b) crosslinking the thermoplastic elastomer; (c) heating a thermoplastic elastomer to a first temperature to soften the thermoplastic elastomer; (d) infusing the thermoplastic elastomer with at least one inert gas at a first pressure sufficient to cause the at least one inert gas to permeate into the softened thermoplastic elastomer; and (e) reducing the pressure to a second pressure lower than the first pressure while the article is softened to at least partially foam the precursor into a foamed article, wherein the foamed article is substantially the same shape as the precursor.)

1. A method of making a foamed article comprising:

a) injection molding the molten thermoplastic elastomer to form a precursor;

b) crosslinking the thermoplastic elastomer;

c) heating the thermoplastic elastomer to a first temperature to soften the thermoplastic elastomer;

d) infusing the thermoplastic elastomer with at least one inert gas at a first pressure sufficient to permeate the at least one inert gas into the softened thermoplastic elastomer; and

e) reducing the pressure to a second pressure lower than the first pressure while the thermoplastic elastomer softens to at least partially foam the precursor into a foamed article;

wherein the foamed article is substantially the same shape as the precursor.

2. The method of claim 1, wherein the volume of the precursor is between 20% and 80% of the volume of the foamed article.

3. A method of making a foamed article comprising:

a) injection molding the molten thermoplastic elastomer to form a precursor;

b) crosslinking said thermoplastic elastomer of said precursor;

c) heating the thermoplastic elastomer to a first temperature to soften the thermoplastic elastomer;

d) infusing the thermoplastic elastomer with at least one inert gas in a pressure vessel at a first pressure, wherein the first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic elastomer and form an infused thermoplastic elastomer;

e) Cooling the infused thermoplastic elastomer to a second temperature that is lower than the first temperature;

f) after cooling, transferring the infused thermoplastic elastomer from the pressure vessel to a location external to the pressure vessel; and

g) heating the infused thermoplastic elastomer to a third temperature at a third pressure to soften the infused thermoplastic elastomer and at least partially foam the infused thermoplastic elastomer, thereby forming the foamed article,

wherein the foamed article is substantially the same shape as the precursor.

4. The method of claim 3, wherein the location external to the pressure vessel is a mold.

5. The method of claim 4, wherein the mold is a localized mold that limits expansion of the infused thermoplastic elastomer in at least one direction, but less than all directions.

6. The method of claim 5, further comprising melting or dissolving the localized mold to release the foamed article from the localized mold.

7. The method of claim 5, further comprising adhesively or physically attaching the localized mold or a portion of the localized mold to the foamed article.

8. The method of claim 7, wherein the foamed article is a midsole component for an article of footwear, and the localized mold or the portion of the localized mold adhesively or physically attached to the foamed article constitutes a layer or component of the midsole component.

9. The method of claim 3, wherein after the infused thermoplastic elastomer is heated to the third temperature at the third pressure while also reducing the pressure to a fourth pressure at the third temperature to further foam the foamed article.

10. A method of making a foamed article comprising:

a) injection molding the molten thermoplastic elastomer to form a precursor;

b) crosslinking said thermoplastic elastomer of said precursor;

c) heating the thermoplastic elastomer to a first temperature to soften the thermoplastic elastomer;

d) infusing the thermoplastic elastomer with at least one inert gas at a first pressure, wherein the first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic elastomer and form an infused thermoplastic elastomer;

e) cooling the infused thermoplastic elastomer to a second temperature that is lower than the first temperature;

f) Heating the infused thermoplastic elastomer to a third temperature to soften the infused thermoplastic elastomer and subjecting the infused thermoplastic elastomer to a third pressure to at least partially foam the infused thermoplastic elastomer to form the foamed article,

wherein the foamed article is substantially the same shape as the precursor.

Technical Field

The present disclosure relates to methods of forming flexible foams and articles made by the methods.

Background

This section provides background information related to the present disclosure that is not necessarily prior art.

Flexible foams are useful, for example, in cushioning, supporting and absorbing impacts in seats and furniture, footwear, packaging, belts, protective gear, and the like. Generally, the foam is formed into sheets or blocks and cut into the desired preformed shape and then finished in the final shape.

The foam midsole of athletic footwear may be made, for example, from cross-linked poly (ethylene-co-vinyl acetate) (EVA), which may be cut from a foam block or sheet, for example. Injection molding is generally not possible because the foam produced by this method must have a high specific gravity in order to be foamed uniformly. In order to mold a new design of foam midsole, a new mold for each size must be made.

Disclosure of Invention

The present application provides the following:

1) a method of making a foamed article, comprising:

a) injection molding the molten thermoplastic elastomer to form a precursor;

b) crosslinking the thermoplastic elastomer;

c) heating the thermoplastic elastomer to a first temperature to soften the thermoplastic elastomer;

d) Infusing the thermoplastic elastomer with at least one inert gas at a first pressure sufficient to permeate the at least one inert gas into the softened thermoplastic elastomer; and

e) reducing the pressure to a second pressure lower than the first pressure while the article is softened to at least partially foam the precursor into a foamed article;

wherein the foamed article is substantially the same shape as the precursor.

2) The method of 1), further comprising:

f) cooling the thermoplastic elastomer to a second temperature; and

g) reducing the pressure to atmospheric pressure.

3) The method of claim 2), wherein the second temperature is ambient temperature.

4) The method of claim 1), wherein the infused thermoplastic elastomer comprises an amount of the absorbed inert gas sufficient to produce at least partial shaping in a subsequent step when the thermoplastic elastomer is again heated to a temperature that softens the elastomer and exposed to an atmospheric pressure that is less than the first pressure.

5) The method of 1), wherein the elastomer is crosslinked using electron beam radiation.

6) The method of 1), wherein the volume of the precursor is between 20% and 80% of the volume of the foamed article.

7) The method of claim 6), wherein the volume of the precursor is between about 30% and 70% of the volume of the foamed article.

8) The method of 1), wherein the surface of the localized mold limits expansion in at least one direction during foaming.

9) A method of making a foamed article, comprising:

a) injection molding a thermoplastic elastomer to form a precursor;

b) crosslinking the thermoplastic polymer using electron beam radiation;

c) placing an insert comprising a thermoplastic polymer in a cavity of the precursor;

d) infusing the precursor and the insert with at least one inert gas; and

e) heating the precursor and the insert to foam the precursor and the insert into a foamed article.

10) The method of claim 9), wherein the inert gas is nitrogen or carbon dioxide.

11) The method of 10), wherein the inert gas is nitrogen.

12) The method of claim 10), wherein the inert gas is carbon dioxide.

13) The method of claim 9), further comprising heating the thermoplastic elastomer to soften the article prior to infusing the thermoplastic elastomer with the inert gas.

14) The method of claim 9), further comprising introducing the at least one inert gas at a first pressure to permeate into the precursor and the insert.

15) The method of 14), further comprising reducing the pressure to a second pressure lower than the first pressure.

16) The method of claim 9), wherein the surface of the localized mold limits foam expansion in at least one direction, but less than all directions.

17) The method of claim 9), wherein the insert is printed into the cavity of the precursor with a 3D printer.

Drawings

The drawings described herein are for illustrative purposes only of selected embodiments (and not all possible implementations), and are not intended to limit the scope of the present disclosure.

FIG. 1 shows a flow chart for manufacturing a foamed article according to an embodiment of the present invention.

FIG. 2 shows a flow chart for manufacturing a foamed article according to an embodiment of the present invention.

FIG. 3 shows a flow chart for manufacturing a foamed article with an insert according to one embodiment of the present invention.

Detailed Description

A method of manufacturing a foamed article, such as a foam component for an article or footwear, includes forming an unfoamed precursor by molding a thermoplastic polymer, and then foaming the precursor to form the foamed article. The precursor may be made by molding a thermoplastic polymer into a desired shape. The thermoplastic polymer may be a thermoplastic elastomer composition. The precursor may have substantially the same shape as the foamed article, but a smaller volume. "substantially" is used herein to indicate that the shape change occurring during the foaming process is small. For example, a 90 ° angle of the precursor may not be as sharp in a foamed article because the angle may become slightly rounded during the foaming process. In some embodiments, the precursor volume is at least 20%, 30%, 40%, 50%, 60%, or 70% of the foamed article volume. In other embodiments, the volume of the precursor is at most 30%, 40%, 50%, 60%, 70%, or 80% of the volume of the foamed article. The precursor and foamed article may be in the shape of a midsole for a shoe. To foam the precursor, the precursor is heated to a first temperature to soften the thermoplastic polymer, and the softened precursor is then infused with at least one inert gas at a first pressure. The first pressure may be greater than atmospheric pressure. The thermoplastic polymer is heated to a temperature sufficient to soften the thermoplastic polymer. The first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer to form an infused softened thermoplastic polymer. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination thereof. The amount of the at least one inert gas infused into the softened thermoplastic polymer member is sufficient to produce at least partial foaming of the softened thermoplastic polymer in a subsequent step in which the infused softened thermoplastic polymer is exposed to a lower pressure. After infusion with the inert gas, the thermoplastic polymer may optionally be cooled to a second temperature and the pressure reduced to atmospheric pressure (e.g., without foaming the thermoplastic polymer) and then heated again to foam the precursor and form a foamed article. The foamed article, for example a foamed member for an article or footwear, may be reheated to a temperature at which the thermoplastic polymer softens to at least partially foam the thermoplastic polymer. The foamed article can be heated under pressure (e.g., at a pressure greater than atmospheric pressure) to a temperature at which the thermoplastic polymer softens and foams as the pressure is reduced, e.g., to atmospheric pressure.

A method of manufacturing a foamed article, such as a foamed member for an article of footwear, includes injection molding a thermoplastic polymer to form a precursor such that the precursor contains a cavity. The thermoplastic polymer may be crosslinked during or after molding. In one embodiment, the precursor may comprise a cavity. An insert comprising a thermoplastic polymer may then be placed in the cavity of the precursor. The insert may be printed into the cavity using a three-dimensional (3D) printer. The insert may comprise the same thermoplastic polymer as the molding precursor or a different thermoplastic polymer. The thermoplastic polymer of the insert and the thermoplastic polymer of the precursor may each independently be a thermoplastic elastomer composition. The thermoplastic polymer of the insert may be crosslinked after placement in the cavity. The precursor and the insert, if present, are then heated such that the respective thermoplastic polymer infused with the at least one inert gas as described above is below or up to the saturation point. In other words, each thermoplastic polymer may be infused with an inert gas at a concentration that is less than or equal to the saturation point. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination thereof. The precursor infused with the gas is depressurized or brought to atmospheric pressure at a temperature at which the precursor (and optionally the insert) at least partially foams. The thermoplastic polymer may be heated to a first temperature at a first pressure and infused with an inert gas, and then the pressure may be reduced to a second pressure less than the first pressure to at least partially foam the thermoplastic polymer. The second pressure may be atmospheric pressure or may be above atmospheric pressure. During foaming, a localized mold may be used to limit expansion in at least one direction. The foamed article may be a midsole of an article of footwear.

The at least partially foamed article may be subjected to a second foaming step as follows: the at least partially foamed article is heated to a second temperature at which the thermoplastic polymer is softened and the softened thermoplastic polymer is infused with at least one inert gas at a third pressure sufficient to permeate the at least one inert gas into the softened thermoplastic polymer, and then the pressure is reduced to a fourth pressure lower than the second pressure to further foam the thermoplastic polymer. The third pressure may be greater than atmospheric pressure. The second temperature may be the same as or different from the first temperature. The at least one inert gas used in the second foaming step may be the same or different from the inert gas used in the original foaming step. Suitable examples of inert gases are again noble gases, nitrogen, carbon dioxide or any combination thereof. The amount of inert gas injected into the thermoplastic polymer may be below or up to the saturation point. The third pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer, and may be the same as or different from the first pressure. The pressure is reduced to a fourth pressure lower than the first pressure to further foam the thermoplastic polymer. The fourth pressure may be the same as or different from the second pressure. The second foaming step can produce a foamed article of lower density. The second foaming step may also be used to further shape the foamed article, for example when the second foaming step is performed in a mold or with a partial mold.

The foamed article may include an insert. The precursor may be molded to have a cavity. An insert may be placed in the cavity. In some embodiments, the insert is printed into the cavity using a 3D printer. The insert may comprise a thermoplastic polymer. In some embodiments, the insert is the same material as the precursor. The insert may also be infused with an inert gas and foamed in a substantially similar proportion as the precursor, or the insert may be a material different from the precursor and may be foamed in a smaller or larger proportion than the precursor is foamed

The foamed article may be incorporated into other articles as a cushioning material. As non-limiting examples, the foamed article may be a foamed element in a shoe (e.g., a portion of an upper), such as a collar, a midsole, or a portion of a midsole, or an outsole or a portion of an outsole; foam pads in shin guards, shoulder pads, chest protectors, face masks, helmets or other head protectors (headgears), knee pads and other protective equipment; an element disposed between fabric layers of an article of apparel; or the foamed article may be used in other known cushioning applications for protection or comfort, such as in pillows, cushions, or in articles or furniture. In various embodiments, the foamed article is a midsole of an article of footwear. The midsole provides cushioning in the footwear. The midsole should be durable, but it is also preferred to add as little weight as possible to the footwear, while still cushioning to the desired degree. In manufacturing the article of footwear, the midsole should also be capable of bonding with the outsole, the upper, or any other component (e.g., sole dimples, bladders, or decorative members).

As used in this specification, "a," "an," "the," "at least one," and "one or more" can interchangeably mean that there is at least one of the items; unless the context clearly indicates otherwise that a plurality of such items are present. All numbers expressing quantities of parameters (e.g., quantities or conditions) used in the specification, including the appended claims, are to be understood as being modified in all instances by the term "about", whether or not "about" actually appears before the value. "about" means that the numerical value recited allows some slight imprecision (with some approach to exactness in the value; approximately or fairly close to the value; nearly). If the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning, then "about" as used herein indicates at least variations that may result from ordinary methods of measuring and using the parameters. Additionally, disclosure of ranges should be understood to specifically disclose all values within the stated range and further divided ranges. The terms "comprises," "comprising," and "having," are inclusive and therefore specify the presence of stated features, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, or components. The order of the steps, procedures, and operations may be changed, where possible, and additional or alternative steps may be employed. As used in this specification, the term "or" includes any and all combinations of the associated listed items.

Fig. 1 shows a flow chart for manufacturing a foamed article according to an embodiment of the present invention. In a first step 110, a thermoplastic elastomer is molded into a precursor of a desired shape. The polymer of the precursor is then crosslinked in step 120. In some embodiments, the polymer is crosslinked in the mold. In some embodiments, crosslinking is performed by irradiation with an electron beam. In step 130, the precursor is then heated to a first temperature to soften the precursor and infused with an inert gas at a first pressure. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination of these. The first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The first exposure is under pressure and for a sufficient duration to allow an amount of gas to penetrate into the softened polymer to cause at least partial foaming when the pressure is reduced. The amount of gas required may depend on factors such as the surface area of the precursor, the type of polymer, the pressure and temperature, etc. The infusion step may continue until the saturation point of the thermoplastic polymer for the gas. The precursor is then cooled to a second temperature in step 140. Finally, in step 150, the pressure is reduced to a second pressure less than the first temperature to cause foaming. The second temperature is a temperature at which the gas does not significantly foam the thermoplastic polymer for a desired length of time. For example, the second temperature may be at or below about 30 ℃. The second pressure may be atmospheric pressure. The article is then at least partially foamed. During step 150, the precursor may optionally be heated to a foaming temperature. The foaming temperature is a temperature that helps to foam the precursor. The foaming temperature may be higher than room temperature.

Fig. 2 shows a flow chart for manufacturing a foamed article according to another embodiment of the present invention. First, in step 210, a precursor is fabricated by molding a thermoplastic elastomer into a desired shape. The polymer is then crosslinked in step 220. The precursor is then heated to a first temperature to soften the precursor and infused with an inert gas at a first pressure in step 230. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination of these. The first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The first exposure is under pressure and for a sufficient duration to allow an amount of gas to penetrate into the softened polymer to cause at least partial foaming when the pressure is reduced. The amount of gas required may depend on factors such as the surface area of the precursor, the type of polymer, the pressure and temperature, etc. The infusion step may continue until the saturation point of the thermoplastic polymer for the gas. The infused precursor is then cooled to a second temperature in step 240. Then, in step 250, the pressure is reduced to a second pressure. In step 260, the precursor is heated to a third temperature while at least partially foaming the precursor at a third pressure. While maintaining at the third temperature, the pressure is reduced to a fourth pressure to cause foaming.

FIG. 3 illustrates a method of manufacturing a foam article with an insert according to one embodiment of the present invention. In step 310, a thermoplastic elastomer is injection molded into a precursor such that the precursor contains a cavity. The precursor may have a cavity to allow an insert to be placed into the precursor. In some embodiments, the molding is performed by another molding technique. Then, in step 320, the thermoplastic polymer is crosslinked. In some embodiments, crosslinking is accomplished using electron beam radiation. In step 330, an insert is placed into the cavity of the precursor. The precursor may comprise one or more cavities for the inserts to be received. In some embodiments, the insert is printed into the cavity. In further embodiments, the insert is printed into the cavity using a 3D printer. Then, in step 340, the precursor and any insert are heated to soften the precursor and the insert, and then an inert gas is introduced into the precursor and the insert at a first pressure. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination of these. The first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The first exposure is under pressure and for a sufficient duration to allow an amount of gas to penetrate into the softened polymer to cause at least partial foaming when the pressure is reduced. The amount of gas required may depend on factors such as the surface area of the precursor, the type of polymer, the pressure and temperature, etc. The infusion step may continue until the saturation point of the thermoplastic polymer for the gas. In step 350, the precursor and the insert are cooled to a second temperature. Finally, in step 360, the pressure is reduced to atmospheric pressure to foam the precursor and the insert. In some embodiments, the precursor may be subjected to an additional foaming step.

The precursor of the foamed article may be formed by molding a thermoplastic polymer (in some embodiments, a thermoplastic elastomer). Molding may be accomplished by injection molding, compression molding, extrusion or other molding processes appropriate to the thermoplastic polymer selected and the shape of the precursor formed. Forming the precursor prior to foaming the article allows the mold or other equipment to be smaller and reduces the amount of waste from the molding process, both of which make the disclosed foaming process more economical, less wasteful, and easier to implement. Foaming an article during the molding step requires a significantly larger mold, which requires more material for manufacture and more energy for use.

A localized mold having a surface that limits foam expansion in at least one direction, but less than all directions, may optionally be used during the foaming step to further control the shape of the final part, e.g., maintain a flat or sharp edge. The partial mold does not completely surround the article during foaming. Since the article is not completely surrounded during foaming, the infused gas present in the article is able to escape from the partial mold from at least a portion of the outer surface of the article. The partial mold may abut the article before foaming begins, or the article may contact a surface of the partial mold during foaming to prevent further expansion of the article in the direction of the surface of the partial mold during foaming. The local mold surface that limits foam expansion may be flat and may optionally include one or more spaces through which the structure may expand out of the surface during foaming. The outer surface of the article prior to foaming may define a top, a bottom opposite the top of the structure, and a perimeter between the top and the bottom, and the surface of the partial mold may limit foam expansion of at least a portion of the perimeter. The surface of the partial mold may limit the expansion of the foam to expand in the direction of the top or the bottom or both the top and the bottom. In another example, the partial mold may have a bottom surface and one or more side surfaces that limit expansion of the foam, and may open in a direction opposite the bottom surface. The partial mold may include a bottom and sides, and the sides may or may not completely surround the article being foamed. The localized mold may have adjacent portions that separate during the foaming of the article. For example, the localized mold may have a first mold part comprising a bottom surface and a second mold part comprising a side surface, wherein the first mold part and the second mold part are adjacent but not joined, in which case the second mold part may be moved away from the first mold part prior to demolding of the foamed article from the second mold part. The localized mold may be in place prior to deposition of the unfoamed thermoplastic polymer onto the support surface to form the article, or may be in place after the three-dimensional printing process but prior to heating the article to permeate the at least one inert gas into the softened article.

In any of these examples, the localized mold may have a surface that imparts a pattern or decoration on at least a portion of the foamed article. In any of these examples, the partial mold may have the shape of a midsole of footwear. The shape may be that of the perimeter of the midsole or a portion of the midsole perimeter. In any of these examples, the localized mold may be of a sacrificial nature that is destroyed upon removal of the molded foamed article. For example, the partial mold or a portion of the partial mold may be cut or torn away after the article is molded. In another example, the localized mold or a portion of the localized mold may be melted or dissolved after the article is molded. In yet another example, the partial mold or a portion of the partial mold may become part of a foamed article, for example, the partial mold or a portion of the partial mold may become a layer or member of a footwear midsole that is foamed and shaped by the partial mold. In such a case, the partial mold or a portion of the partial mold may be adhesively or physically attached during the foaming and molding process.

The molded precursor can be in a desired shape that is substantially the same as the shape of the foamed article. In some embodiments, the precursor may be shaped like a midsole of a shoe. Once the precursor is foamed to full size, the foamed article may be suitable for use as a midsole for a shoe. In other embodiments, the foamed article may be an upper, a collar, a tongue, an insole, a shinguard, a shoulder pad, a chest protector, a face mask, a helmet, a headgear, a knee protector, an article of clothing, a belt, a furniture cushion, or a bicycle seat.

The thermoplastic polymer composition may comprise any thermoplastic polymer, including thermoplastic elastomers suitable for the intended use of the foamed article to be manufactured. Non-limiting examples of suitable thermoplastic polymers and elastomers include ethylene-vinyl acetate copolymers, thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, thermoplastic polyamide elastomers (PEBA or polyether block polyamides), thermoplastic polyester elastomers, metallocene-catalyzed block copolymers of ethylene and-olefins having from 4 to about 8 carbon atoms, and styrene block copolymer elastomers (e.g., poly (styrene-butadiene-styrene), poly (styrene-ethylene-co-butylene-styrene), and poly (styrene-isoprene-styrene)).

The thermoplastic polyurethane elastomer may be selected from thermoplastic polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes, including but not limited to polyurethanes polymerized using polyethers and polyesters, including polycaprolactone polyesters, as the polymeric diol reactant. These polymeric diol-based polyurethanes are prepared by reaction of a polymeric diol (polyester diol, polyether diol, polycaprolactone diol, polytetrahydrofuran diol, or polycarbonate diol), one or more polyisocyanates, and optionally one or more chain extending compounds. Preferably, the polyurethane based on the polymeric diol is substantially linear (i.e., substantially all of the reactants are difunctional). Diisocyanates used to make polyurethane elastomers can be aromatic or aliphatic, and examples include, but are not limited to: isophorone diisocyanate (IPDI), methylenebis-4-cyclohexyl isocyanate (H12MDI), cyclohexyl diisocyanate (CHDI), m-tetramethylxylene diisocyanate (m-TMXDI), p-tetramethylxylene diisocyanate (p-TMXDI), 4 '-methylenediphenyl diisocyanate (MDI, also known as 4,4' -diphenylmethane diisocyanate), 2, 4-or 2, 6-Toluene Diisocyanate (TDI), ethylene diisocyanate, 1, 2-diisocyanatopropane, 1, 3-diisocyanatopropane, 1, 6-diisocyanatohexane (hexamethylene diisocyanate or HDI), 1, 4-butylidene diisocyanate, and the like, which may be used in combination. Chain extending compounds or chain extenders have two functional groups reactive with isocyanate groups such as diols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups such as alkanolamines, aminoalkylthiols, and hydroxyalkylthiols, and the like. The molecular weight of the chain extender may range from about 60 to about 400. Alcohols and amines are generally used. Examples of useful glycols include ethylene glycol and lower oligomers of ethylene glycol including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol and lower oligomers of propylene glycol include dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; cyclohexanedimethanol; 1, 6-hexanediol; 2-ethyl-1, 6-hexanediol; 1, 4-butanediol; 2, 3-butanediol; 1, 5-pentanediol; 1, 3-propanediol; butanediol; neopentyl glycol; and combinations thereof. Suitable diamine chain extenders include, but are not limited to, ethylene diamine, diethylene triamine, triethylene tetramine, and combinations thereof. Other typical chain extenders are amino alcohols such as ethanolamine, propanolamine, butanolamine, and combinations of these.

The polyester diols used to form the thermoplastic polyurethane elastomers are generally prepared by the polycondensation of one or more polyacid compounds and one or more polyol compounds. Preferably, the polyacid compounds and polyol compounds are difunctional, i.e., diacid compounds and diols are used to prepare substantially linear polyester diols, but small amounts of monofunctional, trifunctional, and higher functionality materials (perhaps up to 5 mole percent) may be included to provide a lightly branched but uncrosslinked polyester polyol component. Suitable dicarboxylic acids include, but are not limited to, glutaric acid, succinic acid, malonic acid, oxalic acid, phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, suberic acid, azelaic acid, dodecanedioic acid, their anhydrides and polymerizable esters (e.g., methyl esters) and acid halides (e.g., acid chlorides), and mixtures of these. Suitable polyols include those already mentioned, especially diols. In a preferred embodiment, the carboxylic acid component comprises one or more of adipic acid, suberic acid, azelaic acid, phthalic acid, dodecanedioic acid, or maleic acid (or anhydrides or polymerizable esters of these), and the diol component comprises one or more of 1, 4-butanediol, 1, 6-hexanediol, 2, 3-butanediol, or diethylene glycol. Typical catalysts for the esterification polymerization are protonic acids, Lewis acids, titanium alkoxides and dialkyltin oxides. Polylactones such as polycaprolactone diols may also be used.

Polymeric polyethers can be obtained by reacting a diol initiator, such as 1, 3-propanediol or ethylene glycol or propylene glycol, with an alkylene oxide chain extender. Polyethylene oxide (also known as polyethylene glycol), polypropylene oxide (also known as polypropylene glycol) and block polyethylene oxide-polypropylene oxide copolymers may be used. Two or more different alkylene oxide monomers may be randomly copolymerized by simultaneous addition or polymerized in blocks by sequential addition. Tetrahydrofuran can be polymerized by a cationic ring opening reaction initiated by the formation of a tertiary oxonium ion. Polytetrahydrofuran is also known as polytetramethylene ether glycol (PTMEG).

Aliphatic polycarbonate diols useful for the manufacture of thermoplastic polyurethane elastomers are prepared by reacting a diol with a dialkyl carbonate (e.g., diethyl carbonate), diphenyl carbonate, or dioxolane (e.g., a cyclic carbonate having five-and six-membered rings) in the presence of a catalyst such as an alkali metal, tin catalyst, or titanium compound. Useful diols include, but are not limited to, any of those already mentioned. Aromatic polycarbonates are generally prepared from the reaction of bisphenols, such as bisphenol a, with phosgene or diphenyl carbonate.

The polymeric glycol preferably has a weight average molecular weight of at least about 500, more preferably at least about 1000, and even more preferably at least about 1800 and a weight average molecular weight of up to about 10,000, although polymeric glycols having a weight average molecular weight of up to about 5000, especially up to about 4000, may also be preferred. The polymeric glycol advantageously has a weight average molecular weight in the range of from about 500 to about 10,000, preferably from 1000 to about 5000, more preferably from about 1500 to about 4000. The weight average molecular weight can be determined by ASTM D-4274. The polymeric diol segments typically comprise from about 35% to about 65% by weight of the polyurethane polymer, and preferably from about 35% to about 50% by weight of the polyurethane polymer.

Suitable thermoplastic polyurea elastomers may be prepared by reacting one or more polymeric diamines with one or more of the polyisocyanates already mentioned and one or more of the diamine chain extenders already mentioned. Polymeric diamines include polyoxyethylene diamines, polyoxypropylene diamines, poly (oxyethylene-oxypropylene) diamines and poly (tetramethylene ether) diamines.

Suitable thermoplastic polyamide elastomers can be obtained by the following process: (1) polycondensation of (a) dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid or any other dicarboxylic acid already mentioned with (b) diamines such as ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine or decamethylenediamine, 1, 4-cyclohexanediamine, metaxylylenediamine or any other diamine already mentioned; (2) ring opening polymerization of a cyclic lactam such as caprolactam or laurolactam; (3) polycondensation of aminocarboxylic acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid; or (4) the cyclic lactam is copolymerized with a dicarboxylic acid and a diamine to prepare the carboxylic acid-functional polyamide block, and subsequently reacted with a polymeric ether diol (polyoxyalkylene diol), such as, for example, those such as have been mentioned. The polymerization may be carried out at a temperature of about 180 ℃ to about 300 ℃. Specific examples of suitable polyamide blocks include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, co-nylon, nylon MXD6, and nylon 46.

The thermoplastic polyester elastomer has blocks of low chain length monomer units forming crystalline regions and blocks of soft segments having relatively higher chain length monomer units. Thermoplastic polyester elastomers are commercially available from DuPont under the trade name HYTREL.

Metallocene-catalyzed block copolymers of ethylene and an alpha-olefin having from 4 to about 8 carbon atoms are prepared by single-site metallocene catalysis of ethylene with a softening comonomer, such as hexane-1 or octene-1, for example by a high pressure process in the presence of a catalyst system comprising a cyclopentadienyl-transition metal compound and an aluminoxane (alumoxane). Octene-1 is a preferred comonomer. These materials are commercially available from ExxonMobil under the trade name ExactTM and from Dow Chemical Company under the trade name Engagagne.

Ethylene may also be copolymerized with vinyl acetate to produce ethylene vinyl acetate copolymers. The vinyl acetate content of the copolymer may range from about 5 wt% or 10 wt% up to about 40 wt% or 45 wt% based on the weight of the polymer.

Styrene block copolymer elastomers such as poly (styrene-butadiene-styrene), poly (styrene-ethylene-co-butylene-styrene), and poly (styrene-isoprene-styrene) can be prepared by anionic polymerization, wherein polymer segments are sequentially produced by first reacting an alkyl lithium initiator with styrene, then continuing polymerization by addition with an olefin monomer, and then completing polymerization by addition with styrene again. The S-EB-S and S-EP-S block copolymers are produced by hydrogenation of S-B-S and S-I-S block copolymers, respectively.

In some embodiments, the thermoplastic polymer is crosslinked prior to foaming. The crosslinking process may vary based on the thermoplastic polymer used in the process. In some embodiments, the thermoplastic polymer is crosslinked using radiation, such as Ultraviolet (UV) radiation or electron beam radiation.

The precursor of the thermoplastic polymer is made foamable by heating the thermoplastic polymer to a first temperature to soften the thermoplastic polymer and infusing the softened thermoplastic polymer with at least one inert gas at a first pressure greater than atmospheric pressure, the first pressure being sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination of these. The first pressure is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The first exposure is under pressure and for a sufficient duration to allow an amount of gas to penetrate into the softened polymer to cause at least partial foaming when the pressure is reduced. The amount of gas required may depend on factors such as the surface area of the precursor, the type of polymer, the pressure and temperature, etc. The infusion step may continue until the saturation point of the thermoplastic polymer for the gas.

The precursor with the thermoplastic polymer infused with the inert gas can then be cooled to a second temperature. The second temperature is a temperature at which the gas does not significantly foam the thermoplastic polymer for a desired length of time. For example, the second temperature may be at or below about 30 ℃. The pressure is then reduced to a second pressure. The second pressure may be atmospheric pressure. The precursor is then foamable. The precursor may be removed from the pressure vessel and transferred to another location, such as to a mold at the same building or manufacturing site, or to a remote site, prior to foaming the precursor. The precursor is then foamed by heating the thermoplastic polymer to a third temperature at a third pressure to soften the thermoplastic polymer, causing the thermoplastic polymer to at least partially foam. The third temperature may be the same as or different from the first temperature at which the thermoplastic polymer is infused with the inert gas. Once the third temperature is reached, the pressure is reduced to a fourth pressure or relieved (returned to atmospheric temperature) to foam the thermoplastic polymer.

A precursor having a thermoplastic polymer infused with an inert gas may instead be immediately foamed without intermediate cooling or movement or transfer to a different location, piece of equipment, site, or geographic site. Once the softened thermoplastic polymer has been infused with the at least one inert gas, the pressure is reduced to a second pressure lower than the first pressure to at least partially foam the thermoplastic polymer. The thermoplastic polymer remains softened during foaming. For example, the second pressure may be atmospheric pressure.

When the precursor is foamed, expansion of the precursor in one or more directions, but less than all directions, may be constrained, for example, by placing the article with the thermoplastic polymer precursor adjacent to or in direct contact with a non-yielding surface, such as a localized mold as has been described. The foaming precursor will partially conform to the non-yielding surface and expand in an unconstrained direction when pressed against the surface during foaming.

The foamable thermoplastic polymer can be foamed a second time by repeating the process. The at least partially foamed thermoplastic polymer may be heated to a second temperature to soften the thermoplastic polymer and the softened thermoplastic polymer is again infused with the at least one inert gas at a third pressure sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer, and then the pressure is reduced to a fourth pressure lower than the third pressure while the thermoplastic polymer is softened to further foam the thermoplastic polymer. The third pressure may be greater than atmospheric pressure. The second temperature may be the same as or different from the first temperature at which the thermoplastic polymer is softened and infused during initial foaming. The inert gas used in the second foaming process may be the same as or different from the inert gas used to initially at least partially foam the thermoplastic polymer. The inert gas may be a noble gas, nitrogen, carbon dioxide, or any combination of these. The amount of inert gas infused into the thermoplastic polymer can be up to the saturation point. The third pressure may be the same as or different from the first pressure used during the initial infusion step, so long as it is sufficient to cause the at least one inert gas to permeate into the softened thermoplastic polymer. The pressure may be reduced to a fourth pressure while the thermoplastic polymer softens to further foam the thermoplastic polymer. The fourth pressure may be atmospheric pressure.

Although the foamed article may have an increased volume relative to the precursor, the foamed article may have substantially the same shape as the precursor. In some embodiments, the precursor is at least 20% or at least 30% or at least 40% or at least 50% or at least 60% or at least or 70% by volume of the foamed article. In other embodiments, the precursor volume is at most 30% or at most 40% or at most 50% or at most 60% or at most 70% or at most 80% of the volume of the foamed article.

The precursor may be molded such that the precursor contains a cavity or a plurality of cavities. The insert may then be inserted into the cavity or cavities prior to foaming. The insert may be printed into the cavity using a 3D printer. The insert may be polymeric and may be foamed with the precursor. The insert may comprise the same thermoplastic polymer as the precursor comprises, or may comprise a second thermoplastic polymer different from the thermoplastic polymer of the precursor. The insert may be infused with an inert gas while the precursor is being infused with an inert gas. The insert may then be foamed in substantially the same amount as the precursor ratio, or the insert may be foamed in a different amount than the precursor ratio. The insert may provide aesthetic details or structural support to the foamed article.

In some embodiments, the insert is printed onto the precursor using a 3D printer. Any suitable 3D printer may be used in the method of printing the insert onto the precursor. Examples of suitable printers can be found, for example, in U.S. Pat. No.9,005,710, the subject matter of which is incorporated herein by reference. A 3D printer may be used to print the three-dimensional insert onto the precursor or into the cavity of the precursor. The insert may be the same or different polymeric material as the precursor. In some embodiments, the insert is infused with an inert gas similar to the precursor. In other embodiments, the amount of insert foaming is proportional to the precursor.

Foamed articles that can be made in this manner include uppers, collars, tongues, insoles, midsoles, shin guards, shoulder pads, chest protectors, face masks, helmets, head protectors, knee pads, clothing items, straps, furniture cushions, and bicycle seats.

In various embodiments, the foam article may be used as an insert in another molding process, such as a thermoforming process, or may be joined to other articles by adhesives, fasteners, heat welding, or other means.

The foregoing description of the specific embodiments illustrates features of the invention, but the invention is not limited to any particular embodiment that has been described. Features described with respect to the specific embodiments are interchangeable and can be used together even if not specifically shown or described. The features described may also be varied in many ways. The present invention broadly encompasses such variations and modifications.