Process for producing foam article

Abstract

The present disclosure provides a process. In an embodiment, the process includes providing a foamable composition. The foamable composition includes an ethylene-based elastomer, a blowing agent, and a peroxide. The process includes heating the foamable composition to form a pliable formulation. The pliable formulation has (i) a viscosity (0.1 rad/s at 180 C.) from greater than 70,000 Pa.Math.s to 2,000,000 Pa.Math.s, (ii) a tan delta (0.1 rad/s at 180 C.) from 0.2 to less than 2, (iii) a strain hardening index greater than 2.5 to 6, and (iv) an extensional viscosity (1 s.sup.1 at 180 C.) from greater than 400,000 Pa-s to 7,000,000 Pa-s. The process includes introducing the pliable formulation into a mold having an expandable mold cavity and unidirectionally expanding the expandable mold to form a crosslinked foam article. The process includes cooling, in the expanded mold, the crosslinked foam article; and removing the crosslinked foam article from the expandable mold.

Claims

1. A process comprising: providing a foamable composition comprising an ethylene-based elastomer, a blowing agent, and a peroxide; heating the foamable composition to form a pliable formulation having (i) a viscosity measured at 0.1 rad/s at 180 C. from greater than 70,000 Pa.Math.s to 2,000,000 Pa.Math.s, (ii) a tan delta measured at 0.1 rad/s at 180 C. from 0.2 to less than 2, (iii) a strain hardening index greater than 2.5 to 6, (iv) an extensional viscosity measured at 1 s.sup.1 at 180 C. from greater than 400,000 Pa-s to 7,000,000 Pa-s; introducing the pliable formulation into a mold having an expandable mold cavity; unidirectionally expanding the expandable mold cavity to form a crosslinked foam article; cooling, in the expanded mold cavity, the crosslinked foam article; removing the crosslinked foam article from the expandable mold cavity; and forming a crosslinked foam article having an average aspect ratio from 1.7 to 1.9.

2. The process of claim 1 comprising removing, before the expanding, air from the mold cavity.

3. The process of claim 1 comprising forming the crosslinked foam article having (i) an average cell size from 150 microns to 275 microns, or (ii) a density with skin from 0.170 g/cc to 0.250 g/cc, or (iii) a compression set after 24 hours from 5% to less than 10%, or (iv) a Shore A hardness from 10 to 25, or (v) a rebound resilience from 30% to 50%.

4. The process of claim 3 comprising providing the foamable composition comprising from 88 wt % to 90 wt % of the ethylene-based elastomer that is an ethylene/octene multi-block copolymer having a density from 0.870 g/cc to 0.890 g/cc and a melt index from 1.0 g/10 min to 5.0 g/10 min, the blowing agent, and from 0.5 wt % to 3.0 wt % of the peroxide comprising an organic peroxide; a first step of heating the foamable composition to form the pliable formulation; a second heating step to heat the pliable formulation; introducing the pliable formulation into the mold having the expandable mold cavity; closing the mold and a third heating step to heat the pliable formulation in the closed mold; opening the mold and unidirectionally expanding in the z-axis only the expandable mold cavity to form the crosslinked foam article; and forming the crosslinked foam article having (i) an average cell size 150 microns to 275 microns, and (ii) an average aspect ratio from 1.7 to 1.9, and (iii) a density with skin from 0.170 g/cc to 0.250 g/cc, and (iv) a compression set after 24 hours from 5% to less than 10%, and (v) a Shore A hardness 10 to 25, and (vi) a rebound resilience from 30% to 50%.

5. The process of claim 1 comprising: the heating comprises heating the foamable composition at a temperature of 110 C. for 15 minutes to form the pliable formulation.

6. The process of claim 5 comprising a second step of heating comprises heating the pliable formulation in an oven at a temperature of 110 C. for 15 minutes.

7. The process of claim 6 comprising placing a pre-foamed part in the expandable mold cavity; introducing the pliable formulation in direct contact with the pre-foamed part; and forming the crosslinked foam article directly onto the pre-foamed part.

Description

DETAILED DESCRIPTION

(1) The present disclosure provides a process. In an embodiment, the process includes providing a foamable composition. The foamable composition includes an ethylene-based elastomer, a blowing agent, and a peroxide (and optional additives). The process includes heating the foamable composition to form a pliable formulation having (i) a viscosity (0.1 rad/s at 180 C.) from greater than 70,000 Pa.Math.s to 2,000,000 Pa.Math.s, (ii) a tan delta (0.1 rad/s at 180 C.) from 0.2 to less than 2, (iii) a strain hardening index greater than 2.5 to 6, (iv) an extensional viscosity (1 s.sup.1 at 180 C.) from greater than 400,000 Pa-s to 7,000,000 Pa-s. The process includes introducing the pliable formulation into a mold having an expandable mold cavity and unidirectionally expanding the expandable mold to form a crosslinked foam article. The process includes cooling, in the expanded mold, the crosslinked foam article; and removing the crosslinked foamed article from the expandable mold.
A. Foamable Composition

(2) The process includes providing a foamable composition. The term foamable composition, as used herein, is a mixture of (i) an ethylene-based elastomer, (ii) a blowing agent, (iii) a peroxide, and (iv) optional additives. The final crosslinked foam article is the resultant product of the foamable compositions being subjected to a foaming process.

(3) The ethylene-based elastomer is selected from ethylene vinyl acetate (EVA), polyolefin elastomer, an ethylene/ multi-block copolymer, and combinations thereof.

(4) In an embodiment, the ethylene-based elastomer is an ethylene/-olefin multi-block copolymer. The term ethylene/-olefin multi-block copolymer refers to an ethylene/C.sub.4-C.sub.8 -olefin multi-block copolymer consisting of ethylene and one copolymerizable C.sub.4-C.sub.8 -olefin comonomer in polymerized form (and optional additives), the polymer characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical properties, the blocks joined (or covalently bonded) in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality. Ethylene/-olefin multi-block copolymer includes block copolymer with two blocks (di-block) and more than two blocks (multi-block). The C.sub.4-C.sub.8 -olefin is selected from butene, hexene, and octene. The ethylene/-olefin multi-block copolymer is void of, or otherwise excludes, styrene (i.e., is styrene-free), and/or vinyl aromatic monomer, and/or conjugated diene. When referring to amounts of ethylene or comonomer in the copolymer, it is understood that this refers to polymerized units thereof. In some embodiments, the ethylene/-olefin multi-block copolymer can be represented by the following formula: (AB).sub.n; where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, A represents a hard block or segment, and B represents a soft block or segment. The As and Bs are linked, or covalently bonded, in a substantially linear fashion, or in a linear manner, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymers usually do not have a structure as follows: AAA-AA-BBB-BB. In an embodiment, the ethylene/-olefin multi-block copolymer does not have a third type of block, which comprises different comonomer(s). In another embodiment, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.

(5) In an embodiment, ethylene comprises the majority mole fraction of the whole ethylene/-olefin multi-block copolymer, i.e., ethylene comprises at least 50 wt % of the whole ethylene/-olefin multi-block copolymer. More preferably, ethylene comprises at least 60 wt %, at least 70 wt %, or at least 80 wt %, with the substantial remainder of the whole ethylene/-olefin multi-block copolymer comprising the C.sub.4-C.sub.8 -olefin comonomer. In an embodiment, the ethylene/-olefin multi-block copolymer contains 50 wt % to 90 wt % ethylene, or 60 wt % to 85 wt % ethylene, or 65 wt % to 80 wt % ethylene. For many ethylene/octene multi-block copolymers, the composition comprises an ethylene content greater than 80 wt % of the whole ethylene/octene multi-block copolymer and an octene content of from 10 wt % to 15 wt %, or from 15 wt % to 20 wt % of the whole multi-block copolymer.

(6) The ethylene/-olefin multi-block copolymer includes various amounts of hard segments and soft segments. Hard segments are blocks of polymerized units in which ethylene is present in an amount greater than 90 wt %, or 95 wt %, or greater than 95 wt %, or greater than 98 wt %, based on the weight of the polymer, up to 100 wt %. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10 wt %, or 5 wt %, or less than 5 wt %, or less than 2 wt %, based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments include all, or substantially all, units derived from ethylene. Soft segments are blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than 5 wt %, or greater than 8 wt %, greater than 10 wt %, or greater than 15 wt %, based on the weight of the polymer. In an embodiment, the comonomer content in the soft segments is greater than 20 wt %, greater than 25 wt %, greater than 30 wt %, greater than 35 wt %, greater than 40 wt %, greater than 45 wt %, greater than 50 wt %, or greater than 60 wt % and can be up to 100 wt %.

(7) The soft segments can be present in an ethylene/-olefin multi-block copolymer from 1 wt % to 99 wt % of the total weight of the ethylene/-olefin multi-block copolymer, or from 5 wt % to 95 wt %, from 10 wt % to 90 wt %, from 15 wt % to 85 wt %, from 20 wt % to 80 wt %, from 25 wt % to 75 wt %, from 30 wt % to 70 wt %, from 35 wt % to 65 wt %, from 40 wt % to 60 wt %, or from 45 wt % to 55 wt % of the total weight of the ethylene/-olefin multi-block copolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in, for example, U.S. Pat. No. 7,608,668, entitled Ethylene/-Olefin Block Inter-Polymers, filed on Mar. 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated by reference herein in its entirety. In particular, hard and soft segment weight percentages and comonomer content may be determined as described in column 57 to column 63 of U.S. Pat. No. 7,608,668.

(8) The ethylene/-olefin multi-block copolymer comprises two or more chemically distinct regions or segments (referred to as blocks) joined (or covalently bonded) in a linear manner, that is, it contains chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In an embodiment, the blocks differ in the amount or type of incorporated comonomer, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to block interpolymers of the prior art, including interpolymers produced by sequential monomer addition, fluxional catalysts, or anionic polymerization techniques, the present ethylene/-olefin multi-block copolymer is characterized by unique distributions of both polymer polydispersity (PDI or Mw/Mn or MWD), polydisperse block length distribution, and/or polydisperse block number distribution, due, in an embodiment, to the effect of the shuttling agent(s) in combination with multiple catalysts used in their preparation.

(9) In an embodiment, the ethylene/-olefin multi-block copolymer is produced in a continuous process and possesses a polydispersity index (Mw/Mn) from 1.7 to 3.5, or from 1.8 to 3, or from 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene/-olefin multi-block copolymer possesses Mw/Mn from 1.0 to 3.5, or from 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.

(10) In addition, the ethylene/-olefin multi-block copolymer possesses a PDI (or Mw/Mn) fitting a Schultz-Flory distribution rather than a Poisson distribution. The present ethylene/-olefin multi-block copolymer has both a polydisperse block distribution as well as a polydisperse distribution of block sizes. This results in the formation of polymer products having improved and distinguishable physical properties. The theoretical benefits of a polydisperse block distribution have been previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), pp. 6902-6912, and Dobrynin, J. Chem. Phys. (1997) 107 (21), pp 9234-9238.

(11) In an embodiment, the present ethylene/-olefin multi-block copolymer possesses a most probable distribution of block lengths.

(12) In a further embodiment, the ethylene/-olefin multi-block copolymer of the present disclosure, especially those made in a continuous, solution polymerization reactor, possess a most probable distribution of block lengths. In one embodiment of this disclosure, ethylene/-olefin multi-block copolymers are defined as having: (A) Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, where in the numerical values of Tm and d correspond to the relationship:
Tm>2002.9+4538.5(d)2422.2(d).sup.2, and/or (B) Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, H in J/g, and a delta quantity, T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest Crystallization Analysis Fractionation (CRYSTAF) peak, wherein the numerical values of T and H have the following relationships:
T>0.1299H+62.81 for H greater than zero and up to 130 J/g
T48 C. for H greater than 130 J/g
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 C.; and/or (C) elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/-olefin interpolymer is substantially free of crosslinked phase:
Re>1481-1629(d); and/or (D) has a molecular fraction which elutes between 40 C. and 130 C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/-olefin interpolymer; and/or (E) has a storage modulus at 25 C., G(25 C.), and a storage modulus at 100 C., G(100 C.), wherein the ratio of G(25 C.) to G(100 C.) is in the range of 1:1 to 9:1.

(13) The ethylene/-olefin multi-block copolymer may also have: (F) a molecular fraction which elutes between 40 C. and 130 C. when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to 1 and a molecular weight distribution, Mw/Mn, greater than 1.3; and/or (G) average block index greater than zero and up to 1.0 and a molecular weight distribution, Mw/Mn greater than 1.3.

(14) It is understood that the ethylene/-olefin multi-block copolymer may have one, some, all, or any combination of properties (A)-(G). Block Index can be determined as described in detail in U.S. Pat. No. 7,608,668 herein incorporated by reference for that purpose. Analytical methods for determining properties (A) through (G) are disclosed in, for example, U.S. Pat. No. 7,608,668, col. 31 line 26 through col. 35 line 44, which is herein incorporated by reference for that purpose.

(15) In an embodiment, the ethylene/-olefin multi-block copolymer has hard segments and soft segments, is styrene-free, consists of only (i) ethylene and (ii) a C.sub.4-C.sub.8 -olefin or C.sub.8 -olefin (and optional additives), and is defined as having a Mw/Mn from 1.7 to 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>2002.9+4538.5(d)2422.2(d).sup.2,
where the density, d, is from 0.850 g/cc, or 0.860 g/cc, or 0.870 g/cc to 0.875 g/cc, or 0.877 g/cc, or 0.880 g/cc, or 0.890 g/cc; and the melting point, Tm, is from 110 C., or 115 C., or 120 C. to 125 C., or 130 C., or 135 C.

(16) In an embodiment, the ethylene/-olefin multi-block copolymer is an ethylene/1-octene multi-block copolymer (consisting only of ethylene and octene comonomer) and has one, some, or all of the following properties: (i) a Mw/Mn from 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or (ii) a density from 0.860 g/cc, or 0.865 g/cc, to 0.870 g/cc, or 0.877 g/cc, or g/cc; and/or (iii) a melting point, Tm, from 115 C., or 118 C., or 119 C., or 120 C. to 120 C., or 123 C., or 125 C.; and/or (iv) a melt index (MI) from 0.1 g/10 min, or 0.5 g/10 min to 1.0 g/10 min, or 2.0 g/10 min, or 5 g/10 min, or 10 g/10 min; and/or (v) from 50 to 85 wt % soft segment and from 40 to 15 wt % hard segment (based on total weight of the ethylene/octene multi-block copolymer); and/or (vi) from 10 mol %, or 13 mol %, or 14 mol %, or 15 mol % to 16 mol %, or 17 mol %, or 18 mol %, or 19 mol %, or 20 mol % octene in the soft segment; and/or (vii) from 0.5 mol %, or 1.0 mol %, or 2.0 mol %, or 3.0 mol % to 4.0 mol %, or 5 mol %, or 6 mol %, or 7 mol %, or 9 mol % octene in the hard segment; and/or (viii) an elastic recovery (Re) from 50%, or 60% to 70%, or 80%, or 90%, at 300% min.sup.1 deformation rate at 21 C. as measured in accordance with ASTM D 1708; and/or (ix) a polydisperse distribution of blocks and a polydisperse distribution of block sizes (hereafter referred to as multi-block copolymer properties (i)-(ix)).

(17) In an embodiment, the ethylene/-olefin multi-block copolymer is an ethylene/octene multi-block copolymer. The ethylene/octene multi-block copolymer is sold under the tradename INFUSE, available from The Dow Chemical Company, Midland, Michigan, USA.

(18) The ethylene/-olefin multi-block copolymer can be produced via a chain shuttling process such as described in U.S. Pat. No. 7,858,706, which is herein incorporated by reference. In particular, suitable chain shuttling agents and related information are listed in col. 16 line 39 through col. 19 line 44. Suitable catalysts are described in col. 19 line 45 through col. 46 line 19 and suitable co-catalysts in col. 46 line 20 through col. 51 line 28. The process is described throughout the document, but particularly in col. 51 line 29 through col. 54 line 56. The process is also described, for example, in the following: U.S. Pat. Nos. 7,608,668; 7,893,166; and 7,947,793.

(19) The base ethylene/-olefin multi-block copolymer may include more than one ethylene/-olefin multi-block copolymer.

(20) The foamable composition includes a blowing agent. The blowing agent can be a physical blowing agent or a chemical blowing agent. Nonlimiting examples of suitable physical blowing agent include nitrogen, carbon dioxide, hydrocarbons (e.g., propane), chlorofluorocarbons, noble gasses, and combinations thereof.

(21) In an embodiment, the blowing agent is a chemical blowing agent. The chemical blowing agent generates one or more gasses, by thermal decomposition in the foaming process. Chemical blowing agents include (but are not limited to) sodium bicarbonate, sodium borohydride, azodicarbonamide, azodiisobutyro-nitrile, barium azodicarboxylate, N,N-dimethyl-N,N-dinitrosoterephthalamide, and benzenesulfonhydrazide, 4,4-oxybenzene sulfonyl semicarbazide, 4,4-oxybis(benzenesulfonicacid)dihydrazide, and p-toluene sulfonyl semicarbazide, trihydrazino triazine and mixtures such as those of citric acid and sodium bicarbonate.

(22) In an embodiment, the chemical blowing agent is azodicarbonamide.

(23) The foamable composition includes a peroxide, such as an organic peroxide. The peroxide is the crosslinking agent in the foamable composition. Non-limiting examples of suitable organic peroxide include alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, cyclic peroxides and combinations thereof.

(24) In an embodiment, the organic peroxide is dicumyl peroxide, t-butylisopropylidene peroxybenzene, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, t-butyl-cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-(t-butyl peroxy) hexyne or a combination thereof.

(25) In an embodiment, the organic peroxide is dicumyl peroxide.

(26) The foamable composition includes one or more optional additives. Nonlimiting examples of suitable additives include blowing agent activator (zinc oxide, zinc stearate, zinc sulfide), stability control agent, nucleating agent, filler (talc, calcium carbonate, nanoclay, carbon nanotube, carbon nanofiber), pigment (zinc oxide), antioxidant, an acid scavenger, UV stabilizer, flame retardant, lubricant, processing aid, extrusion aid, and combinations thereof.

(27) The components of the foamable composition are mixed in a mixer or an extruder for uniform dispersion of the blowing agent, peroxide, and optional additive(s) throughout the ethylene-based elastomer matrix. The foamable composition is pelletized, cut into small pieces, or cut into a pre-determined shape for introduction into a mold for foaming.

(28) In an embodiment, the ethylene-based elastomer, chemical blowing agent, organic peroxide, and optional additives are melt-mixed in an internal mixer to melt the polymer and to blend the chemical blowing agent, organic peroxide, and optional additives into the melt-mix. The melt-mix is cut into a pre-determined shape (i.e., a shape to completely cover the bottom of a mold cavity) and introduced into a mold cavity as further described below.

(29) The process includes heating the foamable composition. Heating occurs by placing pellets (or piece(s)) of the foamable composition (i) in an oven, (ii) in a mold, or (iii) a combination of (i) and (ii). Heating is controlled such that heating occurs at sufficient elevated temperature (greater than ambient temperature, or greater than 25 C.) for a sufficient duration of time to form the foamable composition into a pliable formulation so not to decompose the blowing agent and not to decompose the peroxide present in the pliable formulation. Heating of the foamable composition forms a pliable formulation (composed of the components of the foamable composition) and having the following properties: (i) a viscosity (0.1 rad/s at 180 C.) from greater than 70,000 Pa.Math.s to 2,000,000 Pa.Math.s, (ii) a tan delta (0.1 rad/s at 180 C.) from 0.2 to less than 2, (iii) a strain hardening index greater than 2.5 to 6, and (iv) an extensional viscosity (1 s.sup.1 at 180 C.) from greater than 400,000 Pa-s to 7,000,000 Pa-s.

(30) The process includes introducing the pliable formulation into a mold having an expandable mold cavity. As shown in FIG. 1, a mold 10 includes a housing 12 and a movable part 14 in reciprocal and operative communication with housing 12. Movable part 14 moves unidirectionally, that is movement along the z-axis only. The operation between movable part 14 and housing 12 permits no movement in the x-axis and permits no movement in the y-axis. FIG. 1 shows pliable formulation 16 in the mold cavity and movable part 14 in a first position A that is a closed position. With movable part 14 in the closed position, mold 10 is heated to a temperature to kick-off or otherwise initiate the peroxide (a temperature to decompose the peroxide) and kick-off or otherwise initiate the chemical blowing agent (when a chemical blowing agent is used). In an embodiment, pressure (positive pressure or negative pressure) is also applied to the mold cavity when movable part 14 is in the closed position A so as to remove any air present in the mold cavity and/or remove any air present in the pliable formulation 16.

(31) The process includes unidirectionally expanding the expandable mold to form a crosslinked foam article. FIG. 2 shows movable part 14 moved to a second position B, or otherwise an expanded position. Moving movable part 14 to the expanded position B expands, or otherwise increases, the volume of the mold cavity, thereby triggering the pliable formulation to expand and foam. The expanding and foaming pliable formulation fills, or completely fills, the expanded volume of the mold cavity and forms a crosslinked foam article 18. The resultant crosslinked foam article 18 takes the shape of the expanded mold cavity. As mentioned above, movable part 14 moves along the z-axis only, thereby restricting the expansion of the foaming pliable formulation in a single axis, along the z-axis only. During expanding and foaming the pliable formulation 16 (and resultant crosslinked foam article 18) is/are not exposed to the ambient environment. The unidirectional mold expansion forms anisotropic cells in the crosslinked foam article. An anisotropic cell, is a foam cell having an asymmetric shape, whereby the length of the cell is larger in one dimension than the length of the cell in the other dimensions.

(32) The process includes cooling the crosslinked foam article 18 in the expanded mold. Cooling occurs with movable part 14 remaining at expanded position B. Cooling is conducted for a time duration sufficient for the crosslinked foam article to solidify and to set. In an embodiment, the process includes cooling the crosslinked foam article to a temperature from 15 C. to 25 C.

(33) The process forms a crosslinked foam article 18 having one, some, or all of the following properties: (i) an average cell size 150 microns to 275 microns, and/or (ii) an average aspect ratio from 1.5 to 2.0, and/or (iii) a density (with skin) from 0.170 g/cc to 0.250 g/cc, and/or (iv) a compression set (24 hr) 5% to less than 10%, and/or (v) a Shore A hardness 10 to 25, and/or (vi) a rebound resilience 30% to 50%.

(34) In an embodiment, the process includes providing a foamable composition comprising (i) from 88 wt % to 90 wt % of an ethylene-based elastomer that is an ethylene/octene multi-block copolymer having a density from 0.870 g/cc to 0.89 g/cc and a melt index from 1.0 g/10 min to 5.0 g/10 min or 5.0 g/10 min, (ii) a chemical blowing agent, and (iii) from 0.5 wt % to 3.0 wt %, or from 0.7 wt % to 2.7 wt % of an organic peroxide. Weight percent is based on total weight of the foamable composition. The process includes heating the foamable composition to form a pliable formulation having (i) a viscosity (0.1 rad/s at 180 C.) from greater than 70,000 Pa.Math.s to 2,000,000 Pa.Math.s, (ii) a tan delta (0.1 rad/s at 180 C.) from 0.2 to less than 2, (iii) a strain hardening index greater than 2.5 to 6, (iv) an extensional viscosity (1 s.sup.1 at 180 C.) from greater than 400,000 Pa-s to 7,000,000 Pa-s. The process further includes introducing the pliable formulation into a mold having an expandable mold cavity; unidirectionally expanding the expandable mold to form a crosslinked foam article; cooling, in the expanded mold, the crosslinked foam article; and forming a crosslinked foam article having (i) an average cell size 150 microns to 275 microns, or from 200 microns to 260 microns, and/or (ii) an average aspect ratio from 1.5 to 2.0, or from 1.7 to 1.9 and/or (iii) a density (with skin) from 0.170 g/cc to 0.250 g/cc, and/or (iv) a compression set (24 hr) 5% to less than 10%, and/or (v) a Shore A hardness 10 to 25, and/or (vi) a rebound resilience from 30% to 50% (hereafter referred to as foam 1).

(35) In an embodiment, the process includes placing a shoe part (such as a pre-foamed part) in the mold cavity and introducing the pliable formulation with previously-described properties (i)-(iv) on, and in direct contact with, the pre-foamed part. The process includes performing heating, unidirectionally expanding, cooling, and forming a crosslinked foam article (foam 1) directly onto the pre-foamed part. In this way foam 1 is foamed onto, or otherwise fused onto, the pre-foamed part.

(36) The present crosslinked foam article can be molded and shaped as an article of footwear or incorporated into an article of footwear. Nonlimiting examples of suitable footwear articles for the present crosslinked foam article include an outsole, a midsole, an insole, and combinations thereof.

(37) By way of example, and not limitation, some embodiments of the present disclosure are described in detail in the following examples.

Examples

(38) The raw materials used in the preparation for the present crosslinked foam composition, the adhesive layer, and the substrate in the Inventive Examples (IE) are provided in Table 1 below.

(39) TABLE-US-00001 TABLE 1 Starting materials for the foam Component Specification Source INFUSE 9100 Ethylene/octene multi-block copolymer, density: The Dow Chemical Company 0.877 g/cc; MI: 1.0 g/10 min, Tm: 120 C. INFUSE 9500 Ethylene/octene multi-block copolymer, density: The Dow Chemical Company 0.877 g/cc; MI: 5.0 g/10 min, Tm: 122 C. Luperox DC40P Crosslinking agent, Dicumylperoxide ((40%) blended Arkema with an inert filler and scorch protected) Luvobatch BA 5332 Chemical Blowing agent, azodicarbonamide (40%) Lehvoss Omyalite 95T Filler, Ca CO.sub.3 (powder) OMYA AG Switzerland Zinc Oxide (ZnO) Blowing agent activator, CAS: 1314-13-2 Brenntag Schweizerhall AG Zinc Stearate (ZnSt) Blowing agent activator, CAS: 557-05-1 Brenntag Schweizerhall AG
1. Composition Preparation

(40) INFUSE 9100 or INFUSE 9500 (ethylene-based elastomer that is ethylene/octene multi-block copolymer) is added onto a Colin Roll mill with the front roll at 130 C. and the back roll at 125 C. and a rotation speed of 8 rounds per minute (rpm). Zinc oxide, zinc stearate and CaCO.sub.3 filler subsequently are added upon complete melting of the ethylene/octene multi-block copolymer. The blowing agent and peroxide are added last after the fillers and blowing agent activators are uniformly incorporated into the ethylene/octene multi-block copolymer to form the foamable composition. The foamable compositions are provided in Table 2 below.

(41) TABLE-US-00002 TABLE 2 Foamable Compositions Example IE1 IE2 IE3 CS-1 CS-2 CS-3 IE-4/CS-4 IE-5/CS-5 IE-5/CS-6 Component Parts/wt Parts/wt Parts/wt Parts/wt Parts/wt Parts/wt Parts/wt Parts/wt Parts/wt INFUSE 9500 100 100 100 0 0 0 100 100 100 INFUSE 9100 0 0 0 100 100 100 Luperox DC40P- 0.5 1 1.5 2 2.5 3 2 2.5 3 SP2 Luvobatch BA 5 5 5 5 5 5 5 5 5 5332 ZnO 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ZnSt 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Omyalite 95T 5 5 5 5 5 5 CScomparative sample, IEinventive example
2. Foaming Procedure

(42) The foaming procedures for the comparative samples (CS) and the inventive examples (IE) are provided in Table 3 below.

(43) TABLE-US-00003 TABLE 3 Foaming procedures for comparative samples and inventive examples Comparative samples Inventive examples 1. An amount of a CS composition from Table 1 was 1. An amount of an IE composition from Table 1 was weighed to weighed to completely fill the mold volume as shown fill completely the bottom compartment of the mold as shown in in FIG. 1. FIG. 1. The IE composition was heated in the mold for 15 minutes at 110 C. until it was sufficiently pliable and form the IE pliable formulation. 2. The CS composition then was removed from the 2. The IE pliable formulation was transferred to a molding ring mold and was heated for 10 minutes at 110 C. in an (inner diameter of 120 mm and height of 8 mm) and oven to soften and form the CS pliable formulation. compression molded in a Colin Table press P 200E for 5 minutes at 120 C. between silicone paper to form the pre-mold. 3. The mold was heated (to 180 C.) and was treated 3. The pre-mold was heated a second time, this time in an oven with silicone release agent, which was sprayed on the at 110 C. for 15 minutes. hot mold interior surfaces, the release agent cured for 20 minutes to prevent sticking of the foam upon opening of the mold. 4. The CS pliable formulation was removed from the 4. After the second heating, the pre-mold was transferred to oven and placed in the open mold, making sure that the mold and pressed tightly in the mold cavity to ensure the the mold surface was covered as well as possible. absence of air in the mold cavity. 5. The heated mold (180 C.) was closed for 10 5. After closing the mold, the pre-mold was compressed inside minutes to allow for curing and decomposition of the the molding cavity at 180 C. at 150 bar for 11 minutes to allow blowing agent under a pressure of 150 bar. A vacuum for curing and decomposition of the blowing agent. was applied to ensure proper filling of the mold cavity. 6. After 10 minutes, the mold was fully opened upon 6. After 11 minutes, the mold was then opened to an expansion which rapid foam expansion occurred in all directions ratio of 3.75, permitting expansion unidirectionally, in the z-axis (x-axis, y-axis, z-axis), ejecting the foam from the only, as shown in FIG. 2. mold. The crosslinked foam material was recovered and cooled in a fume hood. 7. The mold was cooled to room temperature and the crosslinked foam article removed from the mold.

(44) Table 4 provides properties for foamable compositions, pliable formulations, and inventive crosslinked foam articles and comparative samples.

(45) TABLE-US-00004 TABLE 4 CS-A IE2 IE3 IE4 IE5 IE6 CS-1 wt % wt % wt % wt % wt % wt % wt % Component INFUSE 9500 90.01 89.61 89.21 88.81 88.42 88.03 INFUSE 9100 88.81 Luperox DC40P- 0.45 0.90 1.34 1.78 2.21 2.64 1.78 SP2 Luvobatch BA 4.50 4.48 4.46 4.44 4.42 4.40 4.44 5332 ZnO 0.27 0.27 0.27 0.27 0.27 0.26 0.27 ZnSt 0.27 0.27 0.27 0.27 0.27 0.26 0.27 Omyalite 95T 4.50 4.48 4.46 4.44 4.42 4.40 4.44 Pliable formulation S* (Pa .Math. s) at 0.1 25667.4 71326.2 261771 572573 759010 1192470 1737030 rad/s 180 C. Tandelta at 0.1 3.04 1.38 0.70 0.40 0.34 0.26 0.25 rad/s 180 C. E+ (Pa .Math. s) at H = 2 54976 406300 784150 1731600 2416100 5099500 5393700 180 C. SHI 180 C. 1.04 3.70 2.76 3.36 3.72 5.29 3.95 Foam part Ave cell size 277 257 229 249 206 178 124 Ave aspect ratio 1.60 1.72 1.82 1.88 1.82 1.77 1.63 Density w/skin 0.194 0.226 0.215 0.234 0.234 0.191 Density w/o skin 0.201 0.136 0.134 0.139 0.163 0.178 Compression set 12.2 14.4 24.6 17.9 17.7 15.5 37.0 30 min Compression set 9.1 9.6 8.8 6.5 6.9 8.9 4.2 24 hr Shore A 12.6 15.9 20.4 16.9 20.6 23.6 16.5 Rebound 49.5 45.2 38.5 41.3 39.3 50.8 resilience Split tear 1.4 1.8 1.9 1.9 1.9 CS-2 CS-3 CS-4 CS-5 CS-6 wt % wt % wt % wt % wt % Component INFUSE 9500 88.81 88.42 88.03 INFUSE 9100 88.42 88.03 Luperox DC40P- 2.21 2.64 1.78 2.21 2.64 SP2 Luvobatch BA 4.42 4.40 4.44 4.42 4.40 5332 ZnO 0.27 0.26 0.27 0.27 0.26 ZnSt 0.27 0.26 0.27 0.27 0.26 Omyalite 95T 4.42 4.40 4.44 4.42 4.40 Pliable formulation S* (Pa .Math. s) at 0.1 2369680 2877680 572573 759010 1192470 rad/s 180 C. Tandelta at 0.1 0.19 0.16 0.40 0.34 0.26 rad/s 180 C. E+ (Pa .Math. s) at H = 2 1731600 2416100 5099500 180 C. SHI 180 C. 3.36 3.72 5.29 Foam part Ave cell size 116 104 120 107 94 Ave aspect ratio 1.65 1.66 1.58 1.58 1.61 Density w/skin 0.220 0.255 0.152 0.152 0.174 Density w/o skin 0.187 0.226 0.136 0.142 0.163 Compression set 32.3 24.2 46.2 36.6 22.7 30 min Compression set 5.6 6.6 8.5 6.4 6.7 24 hr Shore A 19.2 24.5 8.7 10.6 14.8 Rebound 49.2 47.5 52.7 51.7 50.8 resilience Split tear 2.0 2.1 1.2 1.5 1.6 IE = inventive example, CS = comparative sample

(46) The present process enables the production of crosslinked foam article using lower levels of peroxide from (0.5 wt % to 3.0 wt %, or from 0.7 wt % to 2.7 wt %) and still achieving suitable foam properties for use in footwear, and for use in midsoles in particular. The present process also produces inventive examples of crosslinked foam article having a greater aspect ratio (1.72-1.88) in combination with greater average cell size (206-257 microns) than the comparative samples (aspect ratio 1.58-1.65 and average cell size 94-277 microns).

(47) The present process enables the production of a crosslinked foam article in a single (one-to-one) foaming step without the need for an additional foam compression step as in a phylon foaming process, for example. A foam part can be placed into the mold cavity, onto which the present pliable formulation is placed and subsequently unidirectionally foamed and crosslinked for direct foaming of the instant crosslinked foam article onto the pre-inserted foam part.

(48) It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.