ADDITIVE MANUFACTURING CARTRIDGES AND PROCESSES FOR PRODUCING CURED

POLYMERIC PRODUCTS BY ADDITIVE MANUFACTURING

FIELD

[0001] The present application is directed to additive manufacturing cartridges, and to processes for producing cured polymeric products by additive manufacturing.

BACKGROUND

[0002] Additive manufacturing (which encompasses processes such as "3D Printing") is a process whereby a three-dimensional article is manufactured (such as by printing) layer by layer from raw material. Certain additive manufacturing processes manufacture an article by building up cross-sectional layers of the article as compared to other so-called subtractive manufacturing processes which require that certain portions of a manufactured article be removed in order to produce the article in its final shape or form. While various additive manufacturing methods have existed since the 1980s, certain of them have been focused upon the use of various plastic polymers such as acrylonitrile butadiene styrene (ABS), polycarbonate (PC), high density polyethylene (HDPE), and high impact polystyrene (HIPS). Another type of additive manufacturing process is roll-to-roll UV-NIL (UV-assisted nanoimprint lithography) which has been used to manufacture various devices including battery separators and organic electronics.

SUMMARY

[0003] The present disclosure is directed to additive manufacturing cartridges and to processes for producing cured polymeric products by additive manufacturing.

[0004] In a first embodiment, an additive manufacturing cartridge is disclosed. The cartridge comprises: (a) an actinic radiation curable polymeric mixture comprising (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P][F]n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; and (b) an oxygen impermeable layer surrounding (a). [0005] In a second embodiment, a process for producing an additive manufacturing cartridge according to the first embodiment is disclosed. The process comprises: providing a cartridge having an oxygen impermeable layer, adding contents comprising (i) and optionally (ii) to the cartridge to produce an additive manufacturing cartridge with the oxygen impermeable layer surrounding the contents wherein the oxygen level of the contents within the oxygen impermeable layer is less than 50 ppm.

[0006] In a third embodiment, a process for producing a cured polymeric product is disclosed. The process comprises: providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure having an atmosphere inside, an interior tank capable of containing a liquid mixture and having an atmosphere above the tank, and an interior support structure; providing to the interior tank a liquid actinic radiation curable polymeric mixture comprising: (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P][F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; (iii) at least one actinic radiation sensitive photoinitiator; (iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinker reactive with F; repeatedly forming upon the interior support structure a layer from the liquid mixture; using actinic radiation to cure each layer, thereby producing a cured polymeric product. According to the third embodiment, at least one of the following has an oxygen level of less than 50 ppm: the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere surrounding the interior support structure, or the atmosphere inside the exterior support structure.

[0007] In a fourth embodiment, a rubber good comprising the cured polymeric product produced according to the process of the third embodiment is disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 shows exemplary closed hollow voids in treads, in cut-away profile with the top being the road-contacting surface. [0009] FIG. 2 shows exemplary overhung voids in treads, in cut-away profile with the top being the road-contacting surface.

[0010] FIG. 3 shows exemplary undercut voids in treads, in cut-away profile with the top being the road-contacting surface.

DETAILED DESCRIPTION

[0011] The present disclosure is directed to additive manufacturing cartridges and to processes for producing cured polymeric products by additive manufacturing.

[0012] In a first embodiment, an additive manufacturing cartridge is disclosed. The cartridge comprises: (a) an actinic radiation curable polymeric mixture comprising (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P][F]n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; and (b) an oxygen impermeable layer surrounding (a).

[0013] In a second embodiment, a process for producing an additive manufacturing cartridge according to the first embodiment is disclosed. The process comprises: providing a cartridge having an oxygen impermeable layer, adding contents comprising (i) and optionally (ii) to the cartridge to produce an additive manufacturing cartridge with the oxygen impermeable layer surrounding the contents wherein the oxygen level of the contents within the oxygen impermeable layer is less than 50 ppm.

[0014] In a third embodiment, a process for producing a cured polymeric product is disclosed. The process comprises: providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure having an atmosphere inside, an interior tank capable of containing a liquid mixture and having an atmosphere above the tank, and an interior support structure; providing to the interior tank a liquid actinic radiation curable polymeric mixture comprising: (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P][F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; (iii) at least one actinic radiation sensitive photoinitiator; (iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinker reactive with F; repeatedly forming upon the interior support structure a layer from the liquid mixture; using actinic radiation to cure each layer, thereby producing a cured polymeric product. According to the third embodiment, at least one of the following has an oxygen level of less than 50 ppm: the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere surrounding the interior support structure, or the atmosphere inside the exterior support structure.

[0015] In a fourth embodiment, a rubber good comprising the cured polymeric product produced according to the process of the third embodiment is disclosed.

Definitions

[0016] The terminology as set forth herein is for description of the embodiments only and should not be construed as limiting the invention as a whole.

[0017] As used herein, the phrase "oxygen impermeable" refers to a material (or layer) having an oxygen transmission rate (OTR) of less than 150 cc/m ² -day-atmosphere. The units can alternatively be stated as cm ³ /m ² over 24 hours (i.e., 1 day) and 1 atmosphere and refer to the transmission of oxygen through a sample of material over the course of 24 hours, at 1 atmosphere of pressure, 23 °C and 0% relative humidity (RH). As those of skill in the art will appreciate, the particular OTR of a layer will generally vary depending upon the thickness of material used in the layer. An oxygen impermeable layer is intended to encompass layers of varying materials and thickness so long as the OTR provided above is met.

[0018] As used herein, the phrase "actinic radiation" refers to electromagnetic radiation capable of producing photochemical reactions.

[0019] As used herein, the phrase "additive manufacturing" refers to the process of joining materials to make objects from 3D model data, usually layer upon layer, as opposed to subtractive manufacturing methodologies.

[0020] As used herein, the term "cartridge" refers to a container that is adapted for or configured for use in an additive manufacturing device. [0021] As used herein, the phrase "chain extender" refers to a monofunctionalized hydrocarbon or hydrocarbon derivative containing a functional group that reacts with a functional end group of the diene polymer chain and adds to the polymer chain, thereby increasing its molecular weight.

[0022] As used herein, the phrase "polyfunctional crosslinker" refers to a hydrocarbon or hydrocarbon derivative containing two or more functional groups which are capable of undergoing a reaction to provide cross-linking between two diene polymer chains or within a diene polymer chain.

[0023] As used herein, the term "hydrocarbon" refers to a compound consisting entirely of carbon and hydrogen atoms.

[0024] As used herein, the phrase "hydrocarbon derivative" refers to a hydrocarbon containing at least one heteroatom (e.g., N, O, S).

[0025] As used herein, the term "mer" or "mer unit" means that portion of a polymer derived from a single reactant molecule (e.g., ethylene mer has the general formula — CH2CH2-).

[0026] As used herein, the term "(meth)acrylate" encompasses both acrylate and methacrylate.

[0027] As used herein, the term "photoinitiator" refers to a compound that generates free radicals. The term "photoinitiator" is used interchangeably herein with the phrase "actinic radiation sensitive photoinitiator."

[0028] As used herein, the term "photosensitizer" refers to a light absorbing compound used to enhance the reaction of a photoinitiator. Upon photoexcitation, a photosensitizer leads to energy or electron transfer to a photoinitiator.

[0029] As used herein, the term "polyfunctionalized" refers to more than one functionalization and includes polymers that have been di-functionalized, tri-functionalized, etc. Generally, functionalization of a polymer may occur at one or both ends of a polymer chain, along the backbone of the polymer chain, in a side chain, and combinations thereof. [0030] As used herein, the term "polymer" refers to the polymerization product of two or more monomers and is inclusive of homo-, co-, ter-, tetra-polymers, etc. Unless indicated to the contrary herein, the term polymer includes oligomers.

[0031] As used herein, the term "void" refers to a portion of a tire tread that is devoid of material (other than air); the term can include grooves or channels extending around all or a portion of the circumference of the tire as well as a pocket or cavity that does not extend around the circumference of the tire.

Additive Manufacturing Cartridge

[0032] As discussed above, the first embodiment disclosed herein is directed to an additive manufacturing cartridge. The cartridge comprises: (a) an actinic radiation curable polymeric mixture comprising (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P] [F]n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; and (b) an oxygen impermeable layer surrounding (a). As further discussed above, the additive manufacturing cartridge is a container adapted or configured for use in an additive manufacturing device. Other types of containers such as may be useful for shipping or storage can optionally be included as part of the overall cartridge. As also discussed above, the processes of the second embodiment include providing a cartridge having an oxygen impermeable layer. Certain embodiments of the processes of the third embodiment (i.e., for producing a cured polymeric product) will include the use of a cartridge having an oxygen impermeable layer. For convenience, aspects of the cartridges of the first-third embodiments are discussed together herein and the following discussion should be understood to apply to any and all of those embodiments unless indicated to the contrary. In certain embodiments of the first-third embodiments, the actinic radiation curable mixture includes the chain extender in the actinic radiation curable polymeric mixture. In certain embodiments of the first-third embodiments disclosed herein, the actinic radiation curable polymeric mixture further comprises (includes): (iii) at least one actinic radiation sensitive photoinitiator; (iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinker reactive with F. In certain embodiments of the first-third embodiments, the actinic radiation curable mixture includes the photosensitizer.

[0033] Generally, the additive manufacturing cartridge can be understood as constituting a package capable of enclosing the contents, i.e., the actinic radiation curable polymeric mixture. According to the first-third embodiments, the shape of the additive manufacturing cartridge may vary; generally the cartridge will be adapted to fit into an additive manufacturing device and/or configured to be removably secured to a printer head (or other device within the additive manufacturing device adapted to dispense the content of the cartridge) of the additive manufacturing device. In certain embodiments of the first-third embodiments, the additive manufacturing cartridge comprises (includes) an opening adapted to interface with the printer head of the additive manufacturing device and allow flow of the actinic radiation curable polymeric mixture into the printer head for use in forming layers and ultimately a cured polymeric product.

[0034] In certain embodiments of the first-third embodiments disclosed herein, the additive manufacturing cartridge comprises at least two separate compartments. In certain such embodiments, a first compartment contains (i) (i.e., polyfunctionalized diene monomer- containing polymer having the formula [P][F]n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different) and when present (ii) (i.e., a chain extender based upon F or reactive with F); and a second compartment contains at least one of (iii) or (iv) (i.e., at least one actinic radiation sensitive photoinitiator or a photosensitizer, respectively), when present (v) (i.e., polyfunctional crosslinker reactive with F), and when present at least a portion of (ii).

[0035] Various combinations of one or more compartments for the cartridges according to the first-third embodiments disclosed herein are envisioned to contain the ingredients of the actinic radiation curable polymeric mixture in its various sub-embodiments (as described below). In certain embodiments of the first-third embodiments, at least two cartridges (or compartments) are utilized, with cartridge or compartment comprising: the polyfunctionalized diene monomer-containing polymer having the formula [P][F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different and chain extender based upon F or reactive with F and the second cartridge or compartment comprising chain extender based upon F or reactive with F along with at least one of an actinic radiation sensitive photoinitiator and a photosensitizer. In certain of the foregoing embodiments, the second cartridge or compartment further comprises a crosslinker reactive with F; alternatively, a third cartridge or com partment comprising a crosslinker reactive with F can be provided. I n certain embodiments, a kit is provided for producing an elastomeric cured product by additive printing comprising at least two cartridges as previously described. I n certain embodiments, the kit comprises at least two cartridges, wherein at least one cartridge comprises a polyfunctionalized diene monomer-containing polymer having the formula [P] [F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different and a chain extender based upon F or compatible with F; and at least a cartridge comprises a chain extender based upon F or compatible with F, at least one of an actinic radiation sensitive photoinitiator and a photosensitizer, and optionally a crosslinker reactive with F. I n certain of the foregoing embodiments of the kit and cartridges, at least one of the first or second cartridge or compartment further comprises at least one filler (as discussed in more detail below).

Oxygen Impermeable Layer

[0036] As discussed above, the additive manufacturing cartridge of the first embodiment disclosed herein comprises (includes) an oxygen impermeable layer surrounding the actinic radiation curable polymeric mixture contents of the cartridge. As also discussed above, the processes of the second embodiment include providing a cartridge having an oxygen impermeable layer. Certain embodiments of the processes of the third embodiment (i.e., for producing a cured polymeric product) will include the use of a cartridge having an oxygen impermeable layer. For convenience, the oxygen impermeable layer of the first-third embodiments are discussed together herein and the following discussion should be understood to apply to any and all of those embodiments unless indicated to the contrary. By surrounding the actinic radiation curable polymeric mixture, the oxygen impermeable layer serves to protect those contents from oxygen during shipping, storage and use. [0037] The oxygen impermeable layer may be made of one or more than one material. When more than one material is utilized, the materials may be layered in various configurations and relative thicknesses, may be mixed together in a type of composite mixture, or may be blended together into one homogenous mixture. The particular material or materials of which the oxygen impermeable layer is comprised may vary. In certain embodiments of the first-third embodiments, the oxygen impermeable layer comprises one or more metals, glass, one or more polymers, or a combination thereof. Non-limiting examples of suitable metals that can be utilized in the oxygen impermeable layer of certain embodiments of the first-third embodiments, include, but are not limited to, aluminum foil, tin foil, copper foil, or a combination thereof. As used herein, the term foil is intended to refer to a metal sheet having a thickness of less than 0.2 mm. Non-limiting examples of suitable polymers that can be utilized in the oxygen impermeable layer of certain embodiments of the first-third embodiments include: ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA, PVOH or PVAI), polyesters (e.g., polyethylene terephthalate or PET, glycol-modified PET, acid-modified PET, poly(ethylene-2,6-naphthalate) or PEN, polybutylene terephthalate or PBT, polytrimethylterephthalate or PTT), polyvinyl chloride polymer (PVC), vinyl chloride copolymer, vinylidene chloride polymer, polyvinylidene chloride (PVdC), polyvinylidene fluoride (PVdF), polyvinylpyridines, polyamines, acrylate polymers (e.g., polyacrylic acid, polyacrylonitrile, polymethacrylic acid, poly(methyl methacrylate, polyacrylamide, polyacrylonitrile), cellulose derivative polymers (carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethyl cellulose), chitosan, polyamines, polyethylene oxide, ethylene vinyl acetate copolymer, and combinations thereof. I n certain embodiments of the first-third embodiments, the oxygen impermeable layer comprises ethylene-vinyl alcohol copolymer (EVOH). I n certain embodiments of the first-third embodiments, the oxygen impermeable layer comprises at least two layers with at least one of those layers comprising a polymer and at least one layer comprising a metal foil; in certain such embodiments the polymer comprises EVOH and the metal foil comprises aluminum, tin, copper, or a combination thereof. I n certain embodiments of the first-third embodiments disclosed herein, the oxygen impermeable layer is flexible in that it is capable of at least partially deforming or collapsing upon evacuation or its contents. In certain embodiments of the first-third embodiments disclosed herein, the oxygen impermeable layer is surrounded by a rigid outer container; the rigid outer container may be useful to protect the cartridge during shipping and storage and may be removable prior to use of the cartridge with an additive manufacturing device. The rigid outer container may or may not be comprised of an oxygen impermeable material. In certain embodiments of the first-third embodiments disclosed herein, the oxygen impermeable layer is flexible and is surrounded by a rigid outer container.

[0038] I n certain embodiments of the first-third embodiments disclosed herein, the oxygen impermeable layer includes one or more fillers which contribute to (increase) the oxygen impermeability of the layer. Non-limiting examples of such fillers include one or more of: calcium carbonate, clay, talc, alumina, magnesium carbonate, or mica. Preferably when a filler is used, it is incorporated into one or more of the polymers, as discussed above.

[0039] As discussed above, the oxygen impermeable layer of the first embodiment and the oxygen impermeable layer according to certain embodiments of the first and second embodiments will be comprised of a material having an oxygen transmission rate (OTR) of less than 150 cc/m ² -day-atmosphere. The units can alternatively be stated as cm ³ /m ² over 24 hours (i.e., 1 day) and 1 atmosphere and refer to the transmission of oxygen through a sample of material (or sample of the layer) over the course of 24 hours, at 1 atmosphere of pressure, 23 °C and 0% relative humidity (RH). As those of skill in the art will appreciate, the particular OTR of a material or layer will generally vary depending upon the thickness of material(s) used and the overall thickness of the layer. An oxygen impermeable layer is intended to encompass layers of varying materials and thickness so long as the OTR provided above is met. I n certain embodiments of the first-third embodiments, the oxygen impermeable layer has an OTR of less than 150 cc/m ² -day-atmosphere (e.g., 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.1, 0.01, 0.001 cc/m ² -day-atmosphere), including less than 140 cc/m ² -day-atmosphere, less than 130 cc/m ² -day-atmosphere, less than 120 cc/m ² -day-atmosphere, less than 110 cc/m ² -day-atmosphere, less than 100 cc/m ² -day-atmosphere, less than 90 cc/m ² -day-atmosphere, less than 80 cc/m ² -day-atmosphere, less than 70 cc/m ² -day-atmosphere, less than 60 cc/m ² -day-atmosphere, less than 50 cc/m ² -day-atmosphere, less than 40 cc/m ² -day-atmosphere, less than 30 cc/m ² -day-atmosphere, less than 20 cc/m ² -day-atmosphere, less than 10 cc/m ² -day-atmosphere, less than 5 cc/m ² -day-atmosphere, or lleessss than 1 cc/m ² -day-atmosphere. An OTR value can be determined by various standardized method and the values referred to herein are intended to refer to and encompass values determined by ASTM method D3895 and ASTM method F1927.

[0040] I n certain embodiments of the first-third embodiments disclosed herein, the additive manufacturing cartridge comprises at least two separate compartments. I n certain such embodiments, a first compartment contains (i) (i.e., polyfunctionalized diene monomer- containing polymer having the formula [P] [F]n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different) and when present (ii) (i.e., a chain extender based upon F or reactive with F); and a second compartment contains at least one of (iii) or (iv) (i.e., at least one actinic radiation sensitive photoinitiator or a photosensitizer, respectively), when present (v) (i.e., polyfunctional crosslinker reactive with F), and when present at least a portion of (ii).

[0041] I n certain embodiments of the first-third embodiments disclosed herein, the oxygen level of the contents contained within the additive manufacturing cartridge (i.e., within the oxygen impermeable layer) is less than 50 ppm (e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30 ppm, 25 ppm, 20 ppm, 15 ppm, 10 ppm, 5 ppm, 1 ppm, or less), including less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm. As discussed below, various methods exist for limiting the oxygen content of the contents within the cartridge so as to achieve these levels including, but not limited to, reducing the oxygen content of the contents by subjecting them to vacuum and/or adding an inert gas to the cartridge prior to adding the contents to the cartridge. According to the foregoing methods, in certain such embodiments, the pressure inside the cartridge will be greater than the ambient pressure (i.e., the pressure outside the cartridge) based upon the addition of an inert gas to the cartridge, in order to reduce the oxygen content prior to adding the contents to the cartridge. Various inert gases such as nitrogen, argon, helium, carbon dioxide, and combinations thereof may be utilized in various embodiments of the first-third embodiments. In certain embodiments of the first-third embodiments the inert gas comprises nitrogen.

Processes For Producing An Additive Manufacturing Cartridge

[0042] As discussed above, the second embodiment disclosed herein is directed to a process for producing an additive manufacturing cartridge according to the first embodiment. The process comprises: providing a cartridge having an oxygen impermeable layer, adding contents comprising (i) and optionally (ii) to the cartridge to produce an additive manufacturing cartridge with the oxygen impermeable layer surrounding the contents wherein the oxygen level of the contents within the oxygen impermeable layer is less than 50 ppm. The cartridge of the second embodiment should be understood to include all of the options and variations as discussed above for the cartridge of the first embodiment. The oxygen impermeable layer of the cartridge constitutes a package capable of enclosing the contents, i.e., the actinic radiation curable polymeric mixture.

[0043] I n certain embodiments of the second embodiment, the process further comprises adding an inert gas to the cartridge prior to adding the contents to the cartridge. Various inert gases such as nitrogen, argon, helium, carbon dioxide, and combinations thereof may be utilized in various embodiments of the processes of the second embodiment. In certain embodiments of the second embodiment the inert gas comprises nitrogen. I n certain embodiments of the second embodiment, prior to adding the contents to the cartridge, the oxygen level within the cartridge is less than 50 ppm (e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30 ppm, 25 ppm, 20 ppm, 15 ppm, 10 ppm, 5 ppm, 1 ppm, or less), including less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm. In certain embodiments of the second embodiment, the oxygen level of the contents is reduced to one of the foregoing levels prior to adding the contents to the cartridge; in certain such embodiments, the oxygen level is reduced by subjecting the contents to a vacuum.

Actinic Radiation Curable Polymeric Mixture

[0044] As discussed above, the first-third embodiments disclosed herein contain (or make use of) an actinic radiation curable polymeric mixture comprising (a) a polyfunctionalized diene monomer-containing polymer having the formula : [P] [F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (b) optionally a chain extender based upon F or reactive with F; (c) at least one actinic radiation sensitive photoinitiator; (d) optionally, a photosensitizer; and (e) a polyfunctional crosslinker reactive with F. Generally, the actinic radiation curable polymeric mixture is suitable for use in additive manufacturing processes which utilize various additive manufacturing devices. The product or article produced by curing the actinic radiation curable polymeric mixture is referred to herein as a cured elastomeric/polymeric product. In certain embodiments according to the first-third embodiments, the actinic radiation curable polymeric mixture is curable by light having a wavelength in the UV to Visible range. In certain embodiments of the first-third embodiments, the actinic radiation (light) has a wavelength of about 320 to less than 500 nm, including about 350 to about 450 nm, and about 365 to about 405 nm. Generally, there are two types of radiation induced curing chemistries: free radical and cationic. Free radical curing involves cross-linking through double bonds, most usually (meth)acrylate double bonds. Cationic curing involves cross-linking through other functional groups, most usually epoxy groups.

Polyfunctionalized Diene Monomer-Containing Polymer

[0045] As discussed above, according to the first-third embodiments disclosed herein, the actinic radiation curable polymeric mixture comprises a polyfunctionalized diene monomer- containing polymer which comprises a diene polymer chain [P]. In certain embodiments of the first-third embodiments, the actinic radiation curable polymeric mixture comprises one type of polyfunctionalized diene monomer-containing polymer and in other embodiments, the mixture comprises more than one type of polyfunctionalized diene monomer-containing polymer. Polyfunctionalized diene monomer-containing polymers can be categorized into different types based upon one or more of: molecular weight, monomer type(s), relative amount of monomer(s), types of functional group(s) (e.g., free radical polymerizable or cationic polymerizable), identity of functional group(s) (as discussed in more detail below), and amount of functional group(s). In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer-containing polymer(s) can be referred to as a pre-polymer since they will react with each other and with a chain extender (when a chain extender is present) to form a higher molecular weight polymer. The diene polymer chain comprises (is based upon) at least one diene monomer. A diene monomer is a monomer having two carbon- carbon double bonds. Various diene monomers exist and are generally suitable for use in preparing the diene polymer chain of the polyfunctionalized diene monomer-containing polymer. In certain embodiments according to the first-third embodiments disclosed herein, the diene polymer chain of the polyfunctionalized diene monomer-containing polymer comprises monomers selected from at least one of: acyclic and cyclic dienes having 3 to about 15 carbon atoms. In certain embodiments according to the first-third embodiments disclosed herein, the diene polymer chain of the polyfunctionalized diene monomer-containing polymer comprises monomers selected from at least one of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-l,3-butadiene, 2-ethyl-l,3-butadiene, 2-methyl-l,3-pentadiene, 3- methyl-l,3-pentadiene, 4-methyl-l,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene, 1,3- cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene, farnescene, and substituted derivatives of each of the foregoing. In certain embodiments of the first-third embodiments, the diene polymer chain of the polyfunctionalized diene monomer-containing polymer comprises 1,3-butadiene monomer, isoprene monomer, or a combination thereof. In certain embodiments of the first-third embodiments, the diene polymer chain of the polyfunctionalized diene-monomer-containing polymer further comprises at least one vinyl aromatic monomer. Non-limiting examples of suitable vinyl aromatic monomers include, but are not limited to, styrene, a-methyl styrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, p-tertbutylstyrene, vinyl catechol-based, and combinations thereof. In certain embodiments of the first-third embodiments, the diene polymer chain of the polyfunctionalized diene monomer-containing polymer comprises a combination of 1,3- butadiene monomer and styrene monomer.

[0046] As discussed above, the term "polyfunctionalized" is used herein to refer to more than one functionalization and includes polymers that have been di-functionalized, tri- functionalized, etc. Generally, functionalization of a polymer may occur at one or both ends of a polymer chain, along the backbone of the polymer chain, and combinations thereof. Generally, each F functional group present in the polyfunctionalized diene monomer-containing polymer may be same or different. In certain embodiments according to the first-third embodiments disclosed herein, the polyfunctionalized diene monomer-containing polymer comprises a di-functionalized polymer having an F functional group at each terminal end of the polymer chain; each F functional group may be the same or different. In certain embodiments according to the first-third embodiments disclosed herein, the polyfunctionalized diene monomer-containing polymer comprises a di-functionalized polymer having a F functional group at one terminal end of the polymer chain and at least one additional F functional group along the backbone of the polymer chain; each F functional group may be the same or different. In certain embodiments according to the first-third embodiments disclosed herein, the polyfunctionalized diene monomer-containing polymer comprises a functionalized polymer having at least three F functional groups, with one at each terminal end of the polymer chain, and at least one along the backbone of the polymer chain; each F functional group may be the same or different.

[0047] Various polyfunctionalized diene monomer-containing polymers are commercially available and may be suitable for use in various embodiments of the first-third embodiments disclosed herein. Non-limiting examples of these include, but are not limited to, Sartomer CN307 polybutadiene dimethacrylate, Sartomer CN301 polybutadiene dimethacrylate and Sartomer CN303 hydrophobic acrylate ester, all available from Sartomer Americas (Exton, Pennsylvania); Ricacryl ^® 3500 methacrylated polybutadiene, Ricacryl ^® 3801 methacrylated polybutadiene, Ricacryl ^® 3100 methacrylated polybutadiene, all available from Cray Valley USA LLC (Exton, Pennsylvania); BAC-45 polybutadiene diacrylate and BAC-15 polybutadiene diacrylate, available from San Esters Corp. (New York, New York); Kuraray UC-102 methacrylated polyisoprene and UC-203 methacrylated polyisoprene, available from Kuraray America Inc. (Pasadena, Texas); Poly bd ^® 600E epoxidized polybutadiene and Poly bd ^® 605E polybutadiene, available from Cray Valley USA LLC (Exton, Pennsylvania). Methods for preparing polyfunctionalized diene monomer-containing polymers are well-known to those of skill in the art and include those using functional initiators, functional terminators and reactions of diol terminated dienes with various functional acid chlorides or with carboxylic acids (through a dehydration reaction). Other methods include the reaction of an oxidant and a carboxylic acid to form a peracid for adding an epoxy group.

[0048] I n certain embodiments of the first-third embodiments, the diene polymer chain of the polyfunctionalized diene monomer-containing polymer comprises: polybutadiene, styrene-butadiene copolymer, polyisoprene, ethylene-propylene-diene rubber (EPDM), styrene- isoprene rubber, or butyl rubber (halogenated or non-halogenated).

[0049] The molecular weight of the polyfunctionalized diene monomer-containing polymer according to the first-third embodiments may vary widely depending upon various factors, including, but not limited to the amount and type of chain extender (if any) that is utilized in the actinic radiation curable polymeric mixture. Generally, higher molecular weight polymers will lead to better properties in the cured article or product, but will also lead to higher viscosities in the overall actinic radiation curable polymeric mixture. Thus, preferred polyfunctionalized diene monomer-containing polymers for use in the mixture will balance molecular weight with its effect on viscosity. I n certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer-containing polymer has a Mn of about 3,000 to about 135,000 grams/mole (polystyrene standard). In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer-containing polymer has a Mn of 3,000 to 135,000 grams/mole (polystyrene standard); including about 5,000 to about 100,000 grams/mole (polystyrene standard); 5,000 to 100,000 grams/mole (polystyrene standard); about 10,000 to about 75,000 grams/mole (polystyrene standard); and 10,000 to 75,000 grams/mole (polystyrene standard). The number average molecular weights (M _n ) values that are discussed herein for the polyfunctionalized diene monomer-containing polymer include the weight contributed by the functional groups (F).

[0050] I n certain embodiments of the first-third embodiments, the cured elastomeric mixture comprises crosslinked polyfunctionalized diene monomer-containing polymer has a Mc (molecular weight between crosslinks) of about 500 to about 150,000 grams/mole, including 500 to 150,000 grams/mole (e.g., 1000, 2500, 5000, 10000, 20000, 25000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 115000, 120000, 130000, 140000 or 150000). The crosslinked molecular weight (M _c ) values that are discussed herein for the polyfunctionalized diene monomer-containing polymer include the weight contributed by the functional groups (F). M _c can be determined in accordance with previously published procedures such as those disclosed in Hergenrother, J ., Appl. Polym. Sci., v. 32, pp. 3039 (1986), herein incorporated by reference in its entirety.

[0051] I n certain embodiments of the first-third embodiments, the molecular weight of the crosslinked polyfunctionalized diene monomer-containing polymer of the cured elastomeric mixture can be quantified in terms of M _r or molecular weight between chain restrictions. In certain embodiments of the first-third embodiments, the cured elastomeric mixture comprises crosslinked polyfunctionalized diene monomer-containing polymer has a Mc (molecular weight between crosslinks) of about 500 to about 150,000 grams/mole, including 500 to 150,000 grams/mole (e.g., 1000, 2500, 5000, 10000, 20000, 25000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 115000, 120000, 130000, 140000 or 150000). The crosslinked molecular weight (M _c ) values that are discussed herein for the polyfunctionalized diene monomer-containing polymer include the weight contributed by the functional groups (F). Generally M _r can be determined according to the procedure described in U.S. Patent Application Publication No. 2012/0174661, herein incorporated by reference in its entirely. More specifically, M _r can be determined according to the following equation :

M _r = pRT(A-A ² )

σ where p is the compound density, σ is stress, R is the gas constant, T is temperature, A is 1+Xe where X is the strain amplification factor from the Guth-Gold equation and the strain (e) is (I- lset)/lset where I is the specimen length at a point on the retraction curve and l _set is the specimen length after retraction to zero stress. A TR or tensile retraction test set consists of at least two tensile retraction tests, each to a progressively higher target extension ratio, Amax, followed immediately by a retraction to a zero stress. Each tensile pull and subsequent retraction are performed at the same testing rate such that a series of extension and retraction curve pairs are obtained. During each retraction, the stress, σ, is measured as a function of extension ratio, A, defining the tensile retraction curve. Testing may be performed in accordance with the procedures outlined in Hergenrother, J., Appl. Polym. Sci., v. 32, pp. 3039 (1986), herein incorporated by reference in its entirety.

[0052] When determining M _r for compounds containing rigid fillers, the enhancement of modulus due to rigid particles should be taken into account in a fashion similar to that of Harwood and Payne, J. Appl. Polym. Sci., v. 10, pp. 315 (1966) and Harwood, Mullins and Payne, J. Appl. Polym. Sci, v. 9, pp. 3011 (1965), both of which are herein incorporated by reference in their entirety. When a filled compound is first stretched in tension to the same stress as its corresponding gum compound (e.g., non-filled compound), subsequent retraction and extension curves are generally very similar to those of the gum compounds when stress is graphed as a function of normalized strain. Normalized strain is defined as the strain at any point on the subsequent extension or retraction curves divided by the maximum strain of the initial extension. For retraction curves in particular, and for maximum strains of natural rubber gum compounds up to and including near breaking strain, this could be applied to a number of filled compounds. The result can be interpreted as evidence of strain amplification of the polymer matrix by the filler, where the average strain the polymer matrix of a filled compound is the same as that in the corresponding gum (non-filled) compound, when the filled and gum compounds are compared at the same stress. Strain amplification X can be determined by the Guth-Gold equation as discussed in Mullins et al., J.Appl. Polym. Sci., vol. 9, pp. 2993 (1965) and Guth et al., Phys. Rev. v. 53, pp. 322 (1938), both of which are herein incorporated by reference in their entirety. After correction of Λ for filler level, neo-Hookean rubber elasticity theory (Shen, Science & Technology of Rubber, Academic Press, New York, 1978, pp. 162-165, herein incorporated by reference) may be applied to an internal segment of the retraction curve from which a molecular weight between chain restrictions of all types, M _r can be calculated according to the above equation. Extension of the same rubber specimen to successively higher Amax provides M _r as a function of Amax.

[0053] Tensile retraction testing can be measured using a special ribbed TR mold to prevent slippage when stretched in tension between clamps of an Instron 1122 tester controlled by a computer (for testing, data acquisition and calculations), as described in Hergenrother, J., Appl. Polym. Sci., v. 32, pp. 3039 (1986). Specimens for testing may be nominally 12 mm wide by 50 mm long by 1.8 mm thick. M _r can be calculated at each of 25 (σ, Λ) pairs, collected from about the middle one-third of the particular retraction curve. M _r values as disclosed herein may be the average of the 25 calculated values. In order to reduce test time, elongations to successively higher Amax can be carried out at successively higher speeds of the Instron crosshead motion. A master TR curve can be obtained by shifting the different test speeds to a standardized testing rate of 5%/minute. High strain (greater than about 40% to 80% elongation) region of the smooth curve obtained may be fitted by a linear equation of the form of M _r =S(Amax-l)+Mc. The fit to strain region at less than 80% elongation may deviate steadily from the M _r line as strains are progressively reduced. The logarithm of such difference between the calculated and observed ve can be plotted versus the lower level of strain to give a linear fit to Ave as a function of (Amax-l). The antilog of the reciprocal of the intercept, m, can be denoted as B (expressed in kg/mole) and relates to the micro-dispersion of the filler. See, U.S. Patent No. 6,384,117, herein incorporated by reference in its entirety. In a similar fashion, the lowest strain deviation can be treated to give a plot of AAve as a function of (Amax-l). The antilog of the reciprocal of the intercept for the process that occurs at strains of less than 6% elongation can be denoted as γ (expressed in kg/mole). These three equations, each with a slope and intercept, can be used to fit the various strain regions of the TR curve can be summed to provide a single master equation that empirically describes the M _r response over the entire range of testing. Experimental constants of the new master equation can be adjusted using ExcelSolver ^® to obtain the best possible fit of the predicted values to the experimental values obtained by TR. Fitting criteria consisting of a slope and an intercept can be determined when the experimental and curve fit values of M _r are compared. The composite equation can allow the transition between each fitted linear region to be independent of the choice of the experimental strains measured and the small mathematical adjusting of the strain range can allow a more precise linear fit of the data to be made.

F functional groups

[0054] As discussed above, F represents a functional group associated with the polyfunctionalized diene monomer-containing polymer. Various types of functional groups F may be suitable for use in certain embodiments of the first-third embodiments disclosed herein. In certain embodiments of the first-third embodiments, these functional groups F can be described as either free radical polymerizable or cationic polymerizable, which is a general description of how the groups react upon exposure to actinic radiation (light) to result in cross- linking or curing. Generally, functional groups that improve curability (cross-linking) by actinic radiation are useful as the functional group F.

[0055] In certain embodiments of the first-third embodiments, the F functional group of the polyfunctionalized diene monomer-containing polymer comprises a free radical polymerizable functionalizing group. In certain embodiments of the first-third embodiments, the F functional group of the polyfunctionalized diene monomer-containing polymer comprises a cationic polymerizable functionalizing group. In certain embodiments of the first-third embodiments, the F functional group of the polyfunctionalized diene monomer-containing polymer comprises a combination of cationic polymerizable and free radical polymerizable functional groups either on the same diene polymer chain or on separate diene polymer chains. Generally, functional groups that are free radical polymerizable have the advantage of reacting faster than cationic polymerizable functionalizing groups, but the disadvantage is being prone to inhibition by oxygen exposure. Generally, functional groups that are cationic polymerizable have the advantage of being resistant to oxygen exposure (i.e., they are not inhibited), but have the disadvantages of being prone to inhibition by water exposure and having a generally slower rate of reaction. The combination of cationic polymerizable and free radical polymerizable functional groups can be advantageous as providing the advantages of each type and minimizing the disadvantages of each alone; an additional advantage of such a combination is to allow for a double network system wherein a crosslink of a first type occurs at a first wavelength and a crosslink of a second type occurs at a second wavelength or a single wavelength is used to activate both types of photoinitators which will create a double network.

[0056] In certain embodiments of the first-third embodiments, each functional group F in the polyfunctionalized diene monomer-containing polymer comprises at least one of: acrylate, methacrylate, cyanoacrylate, epoxide, aziridine, and thioepoxide. In certain embodiments of the first-third embodiments, each functional group F in the polyfunctionalized diene monomer-containing polymer comprises an acrylate or methacrylate. Suitable acrylates or methacrylates may be linear, branched, cyclic, or aromatic. As used herein, the term acrylate should be understood to include both acrylic acid and esters thereof. Similarly, the term methacrylate should be understood to include both methacrylic acid and esters thereof. Various types of acrylates and methacrylates are commonly used and may be suitable for use as the functional group F. In certain embodiments of the first-third embodiments disclosed herein, the function group F comprises at least one of: acrylic acid, methacrylic acid, ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, cyclobutyl (meth)acrylate, (cyano)acrylate, 2-ethylhexyl(meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclopropyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, cyclopentyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, isoheptyl (meth)acrylate, cycloheptyl (meth)acrylate, octyl (meth)acrylate, cyclooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, cyclononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, cyclodecyl (meth)acrylate, undecyl (meth)acrylate, isoundecyl (meth)acrylate, cycloundecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isotridecyl (meth)acrylate, cyclotridecyl (meth)acrylate, tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, cyclotetradecyl (meth)acrylate, pentadecyl (meth)acrylate), isopentadecyl (meth)acrylate, cyclopentadecyl (meth)acrylate, and combinations thereof. In certain embodiments of the first-third embodiments, each functional group F in the polyfunctionalized diene monomer-containing polymer comprises an epoxide or a thioepoxide. In certain embodiments of the first-third embodiments, each functional group F in the polyfunctionalized diene monomer-containing polymer comprises an aziridine, which generally can be considered to be a compound containing the aziridine functional group (a 3- membered heterocyclic group with one amine (-NR-), where R is H, CH ₃ , and two methylenes (- CH ).

[0057] In certain embodiments of the first-third embodiments, the chain extender may be chosen based upon compound having a moiety that is reactive with the F functional group of the polyfunctionalized diene monomer-containing polymer. [0058] In certain embodiments of the first-third embodiments, the chain extender comprises one or more additional functional groups Fl along the backbone of the polymer. Such functional groups may be chosen based upon their contribution to desirable properties in the cured polymeric mixture, the cured elastomeric 3-dimensional article or final product. As a non-limiting example, the Fl functional groups may be selected to interact with one or more fillers such as silica filler, i.e., Fl comprises a silica-reactive functional group. Thus, in certain embodiments of the first-third embodiments the polyfunctionalized diene monomer-containing polymer comprises at least one Fl silica-reactive functional group along its backbone. Non- limiting examples of silica-reactive functional groups include nitrogen-containing functional groups, silicon-containing functional groups, oxygen- or sulfur-containing functional groups, and metal-containing functional groups. Another specific example of a Fl functional group includes phosphorous-containing functional groups.

[0059] Non-limiting examples of nitrogen-containing functional groups that can be utilized as a Fl silica-reactive functional group along the backbone of the polyfunctionalized diene monomer-containing polymer in certain embodiments include, but are not limited to, any of a substituted or unsubstituted amino group, an amide residue, an isocyanate group, an imidazolyl group, an indolyl group, a nitrile group, a pyridyl group, and a ketimine group. The foregoing substituted or unsubstituted amino group should be understood to include a primary alkylamine, a secondary alkylamine, or a cyclic amine, and an amino group derived from a substituted or unsubstituted imine. In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer-containing polymer comprises at least one Fl functional group along its backbone selected from the foregoing list of nitrogen-containing functional groups.

[0060] Non-limiting examples of silicon-containing functional groups that can be utilized as a Fl silica-reactive functional group along the backbone of the polyfunctionalized diene monomer-containing polymer in certain embodiments include, but are not limited to, an organic silyl or siloxy group, and more precisely, the functional group may be selected from an alkoxysilyl group, an alkylhalosilyl group, a siloxy group, an alkylaminosilyl group, and an alkoxyhalosilyl group. Suitable silicon-containing functional groups for use in functionalizing diene-based elastomer also include those disclosed in U.S. Patent No. 6,369,167, the entire disclosure of which is herein incorporated by reference. In certain embodiments of the first- third embodiments, the polyfunctionalized diene monomer-containing polymer comprises at least one Fl functional group along its backbone selected from the foregoing list of silicon- containing functional groups.

[0061] Non-limiting examples of oxygen- or sulfur-containing functional groups that can be utilized as a Fl silica-reactive functional group along the backbone of the polyfunctionalized diene monomer-containing polymer in certain embodiments include, but are not limited to, a hydroxyl group, a carboxyl group, an epoxy group, a glycidoxy group, a diglycidylamino group, a cyclic dithiane-derived functional group, an ester group, an aldehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, a thioepoxy group, a thioglycidoxy group, a thiodiglycidylamino group, a thioester group, a thioaldehyde group, a thioalkoxy group, and a thioketone group. In certain embodiments of the first-third embodiments, the foregoing alkoxy group may be an alcohol-derived alkoxy group derived from a benzophenone. In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer- containing polymer comprises at least one Fl functional group along its backbone selected from the foregoing list of oxygen- or sulfur-containing functional groups.

[0062] Non-limiting examples of phosphorous-containing functional groups that can be utilized as a Fl functional group along the backbone of the polyfunctionalized diene monomer- containing polymer in certain embodiments include, but are not limited to, organophosphorous compounds (i.e., compounds containing carbon-phosphorous bond(s)) as well as phosphate esters and amides and phosphonates. Non-limiting examples of organophosphorous compounds include phosphines including alkyl phosphines and aryl phosphines. In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer- containing polymer comprises at least one Fl functional group along its backbone selected from the foregoing list of phosphorous-containing functional groups. Chain Extender

[0063] As discussed above, the actinic radiation curable polymeric mixture optionally comprises a chain extender based upon F or reactive with F. In other words, in certain embodiments of the first-third embodiments the mixture comprises a chain extender, but it is not considered to be essential in all embodiments. Generally, the chain extender is a hydrocarbon or hydrocarbon derivative that is monofunctionalized with a functional group that reacts with a functional end group of the diene polymer chain of the polyfunctionalized diene monomer-containing polymer and is used to increase the molecular weight of the polyfunctionalized diene monomer-containing polymer (by bonding to one of the F groups of the polymer). Preferably, the chain extender lowers the viscosity of the overall actinic radiation curable polymeric mixture and also acts to increase the molecular weight of the polyfunctionalized diene monomer-containing polymer between crosslinks. In certain embodiments of the first-third embodiments, the chain extender also increases the elongation at break of the cured elastomeric/polymeric mixture that results from actinic radiation curing the polymeric mixture.

[0064] In certain embodiments of the first-third embodiments when the chain extender is present, it comprises a compound that is based upon F. In other words, such a chain extender compound comprises an F group. In certain embodiments of the first-third embodiments when the chain extender is present, it comprises a compound that is based upon F or a compound that is reactive with F. By reactive with F is meant a compound containing a moiety that will bond with the F group of the polyfunctionalized diene monomer-containing polymer.

[0065] As discussed above, in those embodiments of the first-third embodiments where the chain extender is present, it may comprise a hydrocarbon or hydrocarbon derivative with monofunctionality selected from various functional groups either based on F or reactive with F. In certain embodiments of the first-third embodiments when the chain extender is present, it is selected so that the Tg of the chain-extended polyfunctionalized diene monomer-containing polymer is less than about 25 °C, including about -65 °C to about 10 °C. Preferably, the chain extender is selected so that the Tg of the extended polyfunctionalized diene monomer- containing polymer even after crosslinking is less than about 25 °C, including about -65 °C to about 10 °C. In certain embodiments of the first-third embodiments when the chain extender is present, it comprises a compound that has a Mw of about 72 to about 1000 grams/mole, including about 72 to about 500 grams/mole.

[0066] I n certain embodiments of the first-third embodiments, when the chain extender is present, it comprises at least one alkyi (meth)acrylate monomer. In certain such embodiments, the alky (meth)acrylate monomer is com prised of an alkyi chain selected from C2 to about C18 and having a reactive meth(acrylate) head group, termed alkyi functionalized (meth)acrylates; alkyi (meth)acrylate monomers having larger alkyi groups may have a thermal transition, Tm, that is higher than desired. By utilizing as a chain extender a compound/monomer that contains only one functional group (e.g., a (meth)acrylate) it is possible to increase the molecular weight between crosslinks, while reducing the viscosity.

[0067] I n certain embodiments of the first-third embodiments when the F group of the polyfunctionalized diene monomer-containing polymer comprises an acrylate or methacrylate, the chain extender comprises at least one alkyi (meth)acrylate monomer. I n certain such embodiments, the alky (meth)acrylate monomer is at least one monomer selected from C2 to about C18 alkyi functionalized (meth)acrylates; alkyi (meth)acrylate monomers having larger alkyi groups may have a Tg that is higher than desired and may unduly increase the Tg of the overall actinic radiation curable polymeric mixture.

[0068] I n certain embodiments of the first-third embodiments, the total amount of polyfunctionalized diene monomer-containing polymer and chain extender can be considered to be 100 parts by weight; in certain such embodiments, the polyfunctionalized diene monomer-containing polymer is present in an amount of 1-100 parts by weight and the chain extender is present in an amount of 0-99 parts by weight. In other words, the chain extender is optional in certain embodiments. Generally, the relative amounts of polyfunctionalized diene monomer-containing polymer and chain extender can vary greatly because, as discussed above, upon exposure to actinic radiation the chain extender adds to the polymer and increases its molecular weight. As a non-limiting example, when the Mn of the polyfunctionalized diene monomer-containing polymer is relatively low (e.g., about 3,000 grams/mole, polystyrene standard), and the Mw of the chain extender is relatively high (e.g., about 1000 grams/mole), the total amount of polyfunctionalized diene monomer-containing polymer and chain extender can comprise relatively less polymer than chain extender. In certain embodiments of the first- third embodiments, the polyfunctionalized diene monomer-containing polymer is present in an amount of 1-90 parts by weight and the chain extender is present in an amount of 10-99 parts by weight, including 1-80 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 20-99 parts by weight, 1-70 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 30-99 parts by weight, 1-60 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 40-99 parts by weight, 1-50 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 50-99 parts by weight, 1-40 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 60-99 parts by weight, 1-30 parts by weight polyfunctionalized diene monomer- containing polymer and the chain extender is present in an amount of 70-99 parts by weight, 1- 20 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 80-99 parts by weight, 1-10 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 10-99 parts by weight. In certain embodiments of the first-third embodiments, the polyfunctionalized diene monomer-containing polymer is present in an amount of 10-99 parts by weight and the chain extender is present in an amount of 1-90 parts by weight, including 20- 99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-80 parts by weight, 30-99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-70 parts by weight, 40-99 parts by weight polyfunctionalized diene monomer- containing polymer and the chain extender is present in an amount of 1-60 parts by weight, 50- 99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-50 parts by weight, 60-99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-40 parts by weight, 70-99 parts by weight polyfunctionalized diene monomer- containing polymer and the chain extender is present in an amount of 1-30 parts by weight, 80- 99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-20 parts by weight, 90-99 parts by weight polyfunctionalized diene monomer-containing polymer and the chain extender is present in an amount of 1-10 parts by weight.

[0069] In certain embodiments of the first-third embodiments, when the F groups of the polyfunctionalized diene monomer-containing polymer comprise (meth)acrylate and the F groups of the chain extender comprise an alkyl (meth)acrylate, the relative amounts of polymer and chain extender are about 50 parts and 50 parts, respectively, including about 40 to about 60 parts polymer and about 60 to about 40 parts chain extender; 40 to 60 parts polymer and 60 to 40 parts chain extender; about 45 to about 60 parts polymer and about 55 to about 40 parts chain extender; 45 to 60 parts polymer and 55 to 40 parts chain extender; about 50 to about 60 parts polymer and about 40 to about 50 parts chain extender; 50 to 60 parts polymer and 40 to 50 parts chain extender; about 55 to about 60 parts polymer and about 40 to about 45 parts chain extender; and 55 to 60 parts polymer and 40 to 45 parts chain extender.

[0070] In certain embodiments of the first-third embodiments, in addition to being monofunctionalized with at least one F group or a functional group reactive with F, the chain extender is further functionalized with at least one functional group F2 that is molecular oxygen reactive. Non-limiting examples of suitable F2 groups include various amines, including, but not limited to, tertiary amines, secondary amines, and primary amines; thiols; silanes; phosphites, tin-containing compounds, lead containing compounds, and germanium-containing compounds. Incorporating at least one molecular oxygen reactive F2 functional group into the chain extender reduces the amount of undesirable oxidation that may otherwise occur from either solubilized oxygen within the actinic radiation curable polymeric mixture or atmospheric oxygen. Without being bound by theory, a functional group F2 that is molecular oxygen reactive can react with any peroxy radicals that are generated (e.g., from the reaction of a free radical with molecular oxygen) to create a new initiator by hydrogen absorption; this reaction avoid or minimizes the undesirable reaction between a peroxy radical and an initiator (which will yield a non-productive product and consume the initiator). The amount of F2 functionalization on the chain extender may vary. I n certain embodiments of the first-third embodiments, the chain extender is about 10 to 100% functionalized with at least one functional group F2 that is molecular oxygen reactive, including 10 to 100% functionalized, about 20 to 100% functionalized, 20 to 100% functionalized, about 30 to 100 % functionalized, 30 to 100% functionalized, about 40 to 100% functionalized, 40 to 100% functionalized, about 50 to 100% functionalized, 50 to 100% functionalized, about 10 to about 90% functionalized, 10 to 90% functionalized, about 10 to about 80% functionalized, 10 to 80% functionalized, about 10 to about 70% functionalized, 10 to 70% functionalized, about 10 to about 60% functionalized, 10 to 60% functionalized, about 10 to about 50% functionalized, and 10 to 50% functionalized. I n other embodiments, in addition to comprising at least one functional group F2 that is molecular oxygen reactive or as an alternative to comprising at least one functional group F2 that is molecular oxygen reactive, a separate molecular oxygen reactive ingredient can be utilized in the actinic radiation curable polymeric mixture. Generally, this separate ingredient comprises a hydrocarbon or hydrocarbon derivative functionalized with at least one of the functional groups discussed above for F2.

Photoinitiator

[0071] As discussed above, the actinic radiation curable polymeric mixture comprises at least one actinic radiation sensitive photoinitiator. I n certain embodiments of the first-third embodiments, the polymeric mixture comprises two, three, or more one actinic radiation sensitive photoinitiators. Generally, the purpose of the photoinitiator is to absorb actinic radiation (light) and generate free radicals or a Lewis acid that will react with the functional groups of the polymer resulting in polymerization. Two types of actinic radiation sensitive photoinitators exist: free radical and cationic. Free radical photoinitiators can themselves be separated into two categories, those that undergo cleavage upon irradiation to generate two free radicals (e.g., benzoins, benzoin ethers, and alpha-hydroxy ketones) and those that form an excited state upon irradiation and then abstract an atom or electron from a donor molecule which itself then acts as the initiating species for polymerization (e.g., benzophenones). In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator comprises at least one free radical photoinitiator. In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator comprises at least one cationic photoinitiator. In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator comprises a combination of at least one free radical photoinitiator and at least one cationic photoinitiator.

[0072] When a photoinitiator is utilized, various photoinitiators are suitable for use in the actinic radiation curable polymeric mixtures. In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator comprises at least one of: a benzoin, an aryl ketone, an alpha-amino ketone, a mono- or bis(acyl)phosphine oxide, a benzoin alkyl ether, a benzil ketal, a phenylglyoxalic ester or derivatives thereof, an oxime ester, a per-ester, a ketosulfone, a phenylglyoxylate, a borate, and a metallocene. In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator comprises at least one of: a benzophenone, an aromatic a-hydroxyketone, a benzilketal, an aromatic a-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, a bis-acylphosphinoxide, and a tris- acylphosphinoxide. In certain embodiments of the first-third embodiments disclosed herein, the photoinitiator is selected from benzophenone, benzildimethylketal, 1-hydroxy-cyclohexyl- phenyl-ketone, l-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-propan-l one, 2-hydroxy- l-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-met hyl-propan-l-one, (4- methylthiobenzoyl)-l-methyl-l-morpholinoethane, (4-morpholinobenzoyl)-l-benzyl-l- dimethylaminopropane, (4-morpholinobenzoyl)-l-(4-methylbenzyl)-l-dimethylaminoprop ane, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl- pentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2-hydroxy-l- {l-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-l,3,3-trimethyl -indan-5-yl}-2-methyl-propan-l- one, 1,2-octanedione, l-[4-(phenylthio)phenyl]-,2-(0-benzyloxime), oligo[2-hydroxy-2-methyl- l-[4-methylvinyl]phenyl]propanone, 2-hydroxy-2-methyl-l-phenyl propan-l-one, and combinations thereof.

[0073] The amount of actinic radiation sensitive photoinitiator(s) utilized can vary. In certain embodiments of the first-third embodiments disclosed herein, when the photoinitiator is present, the actinic radiation curable polymeric mixture comprises about 1 to about 10 parts by weight of the photoinitiator, including about 2 to about 5 parts by weight (all amounts based upon 100 total parts of polyfunctionalized diene monomer-containing polymer and chain extender). The foregoing amounts should be understood to apply to both free radical and cationic photoinitiators and to refer to the total amounts (by weight) of all photoinitiators used in the actinic radiation curable polymeric mixture.

Photosensitizer

[0074] As discussed above, in certain embodiments of the first-third embodiments, the actinic radiation curable polymeric mixture comprises a photosensitizer. In other words, in certain embodiments of the first-third embodiments, the photosensitizer is optional. Generally, the "photosensitizer" is a light absorbing compound used to enhance the reaction of a photoinitiator; it may absorb part of the actinic radiation (light) that the photoinitiator cannot absorb and transfer the energy to the photoinitiator. Upon photoexcitation, a photosensitizer leads to energy or electron transfer to a photoinitiator.

[0075] In those embodiments of the first-third embodiments where a photosensitizer is used, the amount of photosensitizer utilized can vary. (As discussed above, the photosensitizer is not necessarily present in every embodiment disclosed herein.) In certain embodiments of the first-third embodiments disclosed herein, when the photosensitizer is present, the actinic radiation curable polymeric mixture comprises about 0.1 to about 5 parts by weight of the photosensitizer, including about 0.1 to about 2 parts by weight (all amounts based upon 100 total parts of polyfunctionalized diene monomer-containing polymer and chain extender).

[0076] When a photosensitizer is utilized, various photosensitizers are suitable for use in the actinic radiation curable polymeric mixtures. In certain embodiments of the first-third embodiments disclosed herein, the photosensitizer comprises at least one of a ketocoumarin, a xanthone, a thioxanthone, a polycyclic aromatic hydrocarbon, and an oximester derived from aromatic ketone. Exemplary ketocoumarins are disclosed in Tetrahedron 38, 1203 (1982), and U.K. Patent Publication 2,083,832 (Specht et al.). Crosslinker

[0077] As discussed above, the actinic radiation curable mixture comprises a polyfunctional crosslinker reactive with the functional group F of the polyfunctionalized diene monomer-containing polymer. Generally, the polyfunctional crosslinker functions to increase the amount of crosslinking within each diene polymer chain of the polyfunctionalized diene monomer-containing polymer, between (separate) diene polymer chains of polyfunctionalized diene monomer-containing polymers, or both, thereby forming a network. Generally, an increased amount of crosslinker or crosslinking will lower the Mc of the crosslinked (cured) polyfunctionalized diene monomer-containing polymer, thereby resulting in a higher modulus and a lower Eb. In certain embodiments of the first-third embodiments, the polyfunctional crosslinker is a hydrocarbon or hydrocarbon derivative polyfunctionalized with a functional group F. In other words, such a crosslinker comprises multiple F groups. In certain embodiments of the first-third embodiments, the crosslinker is a hydrocarbon or hydrocarbon derivative polyfunctionalized with a functional group F or a functional group that is reactive with F. By reactive is meant a moiety that will bond with at least two F groups of the polyfunctionalized diene monomer-containing polymer.

[0078] Generally, the crosslinker is a polyfunctionalized hydrocarbon or hydrocarbon derivative containing at least two functional groups reactive with F. In certain embodiments of the first-third embodiments, the crosslinker is di-functional and in other embodiments, the crosslinker is tri-functional, tetra-functional, or further functionalized. While the crosslinker is based upon a hydrocarbon or hydrocarbon derivative, it should be understood that it can also be polymer-like in that it can comprise either a single base unit or multiple, repeating base units.

[0079] Various compounds are suitable for use as the crosslinker. In certain embodiments of the first-third embodiments, the crosslinker contains at least two (meth)acrylate functional groups. In certain embodiments of the first-third embodiments, the crosslinker comprises a polyol (meth)acrylate prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms; in such embodiments, the functional group of the crosslinker is (meth)acrylate. Various crosslinkers comprising at least two (meth)acrylate groups are commercially available. In certain embodiments of the first-third embodiments, the crosslinker comprises at least one of the following: Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetraacrylate, Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate, Acrylated epoxidized soybean oil, Ditrimethylol Propane Tetraacrylate, Di-pentaerythritol Polyacrylate, Di- pentaerythritol Polymethacrylate, Di-pentaerythritol triacrylate, Di-pentaerythritol trimethacrylate, Di-pentaerythritol tetracrylate, Di-pentaerythritol tetramethacrylate, Di- pentaerythritol pent(meth)acrylate, Di-pentaerythritol hexa(meth)acrylate, Pentaerythritol Poly(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylated glycerine triacrylate, ε-Caprolactone ethoxylated isocyanuric acid triacrylate and Ethoxylated isocyanuric acid triacrylate, Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate, ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol di(meth)acrylate, ethyleneglycol dimethacrylate (EDMA), polyethyleneglycol di(meth)acrylates, polypropyleneglycol di(meth)acrylates, polybutyleneglycol di(meth)acrylates, 2,2-bis(4- (meth)acryloxyethoxyphenyl) propane, 2,2-bis(4- (meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane) tetra(meth)acrylate, and combinations thereof.

[0080] In certain embodiments of the first-third embodiments, the crosslinker comprises a polyallylic compound prepared from an aliphatic diol, triol or tetraol containing 2- 100 carbon atoms. Exemplary polyallylic compounds useful as crosslinker include those compounds comprising two or more allylic groups, non-limiting examples of which include triallylisocyanurate (TAIC), triallylcyanurate (TAC), and the like, and combinations thereof.

[0081] In certain embodiments of the first-third embodiments, the crosslinker comprises epoxy functional groups, aziridine functional groups, vinyl functional groups, allyl functional groups, or combinations thereof.

[0082] In certain embodiments of the first-third embodiments, the crosslinker comprises a polyfunctional amine with at least two amine groups per molecule. In certain such embodiments, the polyfunctional amine is an aliphatic amine. Exemplary polyfunctional amines include, but are not limited to, diethylene triamine, ethylene diamine, triethylene tetramine, tetraethylene pentamine, hexamethylerie diamine, 1,2-diaminocyclohexane, amino ethyl piperazine, and the like, and combinations thereof.

[0083] In certain embodiments of the first-third embodiments, the polyfunctional crosslinker comprises a combination of two types of functional groups, i.e., a functional group capable of crosslinking at least two diene polymer chains based upon cationic radiation and a functional group capable of crosslinking at least two diene polymer chains based upon free radical radiation. The combination of two types of functional groups may be present on the same polyfunctional crosslinker or on separate crosslinkers (i.e., each with one type of functional group). In certain embodiments of the first-third embodiments, the polyfunctional crosslinker comprises a combination of at least one functional group selected from acrylate groups, methacrylate groups, polyallylic groups, and polyfunctional amines with at least one functional group selected from epoxy groups, aziridine groups, vinyl groups, and allyl groups.

Filler(s)

[0084] In certain embodiments of the first-third embodiments, the actinic radiation curable polymeric mixture further comprises at least one filler; in certain such embodiments, the at least one filler comprises a reinforcing filler, preferably a non-carbon black reinforcing filler (i.e., a reinforcing filler other than carbon black). In certain embodiments of the first-third embodiments, when at least one filler is utilized it comprises a non-carbon black filler (i.e., no carbon black filler is included in the at least one filler). As used herein, the term "reinforcing filler" is used to refer to a particulate material that has a nitrogen absorption specific surface area (N ₂ SA) of more than about 100 m ² /g, and in certain instances more than 100 m ² /g, more than about 125 m ² /g, more than 125 m ² /g, or even more than about 150 m ² /g or more than 150 m ² /g. Alternatively or additionally, the term "reinforcing filler" can also be used to refer to a particulate material that has a particle size of about 10 nm to about 50 nm (including 10 nm to 50 nm). In certain embodiments of the first-third embodiments, the at least one filler comprises a non-carbon black reinforcing filler having a surface area of more than 150 m ² /g, more than 200 m ² /g, more than 250 m ² /g, more than 300 m ² /g, more than 350 m ² /g, more than 400 m ² /g, 150-400 m ² /g, 150-350 m ² /g, 200-400 m ² /g, or 200-350 m ² /g. In certain embodiments of the first-third embodiments, the actinic radiation curable polymeric mixture further comprises at least one metal or metal oxide filler. In other words, the mixture further comprises at least one metal filler, at least one metal oxide filler, or combinations thereof. Various metal fillers and metal oxide fillers are suitable for use in various embodiments of the actinic radiation curable polymeric mixture. In certain embodiments of the first-third embodiments, the at least one metal or metal oxide filler comprises at least one of: silica (in its various forms only some of which are listed below), aluminum hydroxide, starch, talc, clay, alumina (Al ₂ 0 ₃ ), aluminum hydrate (AI ₂ 0 ₃ H ₂ 0), aluminum hydroxide (AI(OH) ₃ ), aluminum carbonate (AI ₂ (C0 ₃ ) ₂ ), aluminum nitride, aluminum magnesium oxide (MgOAI ₂ 0 ₃ ), aluminum silicate (AI ₂ Si0 ₅ , AI ₄ .3Si0 ₄ .5H ₂ 0 etc.), aluminum calcium silicate (AI ₂ 0 ₃ .Ca0 ₂ Si0 ₂ , etc.), pyrofilite (AI ₂ 0 ₃ 4Si0 ₂ .H ₂ 0), bentonite (AI ₂ 0 ₃ .4Si0 ₂ .2H ₂ 0), boron nitride, mica, kaolin, glass balloon, glass beads, calcium oxide (CaO), calcium hydroxide (Ca(OH) ₂ ), calcium carbonate (CaC0 ₃ ), magnesium carbonate, magnesium hydroxide (MH(OH) ₂ ), magnesium oxide (MgO), magnesium carbonate (MgC0 ₃ ), magnesium silicate (Mg ₂ Si0 ₄ , MgSi0 ₃ etc.), magnesium calcium silicate (CaMgSi0 ₄ ), titanium oxide, titanium dioxide, potassium tita nate, barium sulfate, zirconium oxide (Zr0 ₂ ), zirconium hydroxide [Zr(OH) ₂ .nH ₂ 0], zirconium carbonate [Zr(C0 ₃ ) ₂ ], crystalline aluminosilicates, zinc oxide (i.e., reinforcing or non-reinforcing), and combinations thereof, graphite, clay, titanium dioxide, magnesium dioxide, aluminum oxide (Al ₂ 0 ₃ ), silicon nitride, calcium silicate (Ca ₂ Si0 ₄ , etc.), crystalline aluminosilicates, silicon carbide, single walled carbon nanotubes, double walled carbon nanotubes, multi wa lled carbon nanotubes, grapheme oxide, graphene, silver, gold, platinum, copper, strontium titanate (StTi0 ₃ ), barium titanate (BaTi0 ₃ ), silicon (Si), hafnium dioxide (Hf0 ₂ ), manganese dioxide (Mn0 ₂ ), iron oxide (Fe ₂ 0 ₄ or Fe ₃ 0 ₄ ), cerium dioxide (Ce0 ₂ ), copper oxide (CuO), indium oxide (ln ₂ 0 ₃ ), indium tin oxide (ln ₂ 0 ₃ Sn0 ₂ ). I n certain embodiments of the first-third embodiments, the at least one filler comprises at least one of: silica (in its various forms only some of which are listed below), aluminum hydroxide, starch, talc, clay, alumina (Al ₂ 0 ₃ ), aluminum hydrate (AI ₂ 0 ₃ H ₂ 0), aluminum hydroxide (AI(OH) ₃ ), aluminum carbonate (AI ₂ (C0 ₃ ) ₂ ), aluminum nitride, aluminum magnesium oxide (MgOAI ₂ 0 ₃ ), aluminum silicate (AI ₂ Si0 ₅ , AI ₄ .3Si0 ₄ .5H ₂ 0 etc.), aluminum calcium silicate (AI ₂ 0 ₃ .Ca0 ₂ Si0 ₂ , etc.), pyrofilite (AI ₂ 0 ₃ 4Si0 ₂ .H ₂ 0), bentonite (AI ₂ 0 ₃ .4Si02.2H ₂ 0), boron nitride, mica, kaolin, glass balloon, glass beads, calcium oxide (CaO), calcium hydroxide (Ca(OH) ₂ ), calcium carbonate (CaC0 ₃ ), magnesium carbonate, magnesium hydroxide (MH(OH) ₂ ), magnesium oxide (MgO), magnesium carbonate (MgC0 ₃ ), magnesium silicate (Mg ₂ Si0 ₄ , MgSi0 ₃ etc.), magnesium calcium silicate (CaMgSi0 ₄ ), titanium oxide, titanium dioxide, potassium titanate, barium sulfate, zirconium oxide (Zr0 ₂ ), zirconium hydroxide [Zr(OH) ₂ .nH ₂ 0], zirconium carbonate [Zr(C0 ₃ ) ₂ ], crystalline aluminosilicates, zinc oxide (i.e., reinforcing or non-reinforcing), and combinations thereof, graphite, clay, titanium dioxide, magnesium dioxide, aluminum oxide (Al ₂ 0 ₃ ), silicon nitride, calcium silicate (Ca ₂ Si0 ₄ , etc.), crystalline aluminosilicates, silicon carbide, single walled carbon nanotubes, double walled carbon nanotubes, multi walled carbon nanotubes, grapheme oxide, graphene, silver, gold, platinum, copper, strontium titanate (StTi0 ₃ ), barium titanate (BaTi0 ₃ ), silicon (Si), hafnium dioxide (Hf0 ₂ ), manganese dioxide (Mn0 ₂ ), iron oxide (Fe ₂ 0 ₄ or Fe ₃ 0 ₄ ), cerium dioxide (Ce0 ₂ ), copper oxide (CuO), indium oxide (ln ₂ 0 ₃ ), indium tin oxide (l n ₂ 0 ₃ Sn0 ₂ ).

[0085] I n certain embodiments of the first-third embodiments, the at least one filler includes ground, cured rubber, optionally in combination with one of more of the foregoing fillers. As used herein, the term "ground, cured rubber" refers to cured, i.e., vulcanized (cross- linked) rubber that has been ground or pulverized into particulate matter; various particle size ground, cured rubber may be utilized. I n certain embodiments of the first-third embodiments where ground, cured rubber is utilized, it has an average particle size in the range of about 50 μιη to about 250 μιη (including 50 μιη to 250 μιη), preferably an average particle size of about 74 μιη to about 105 μιη (including 74 μιη to 105 μιη. The average particle size of ground, cured rubber particles may be measured by any conventiona l means known in the art including the methods according to ASTM D5644. Examples of suitable sources of rubber for the ground, cured rubber include used tires. It is well known to those skilled in the art that tires are prepared from natural and synthetic rubbers that are generally compounded using fillers including carbon black and sometimes also including silica. The source of the ground, cured rubber used in accordance with the first, second, and third embodiments disclosed herein may vary, but in certain embodiments can be tires (or rubber from such tires) produced with a carbon black filler, with a silica filler, or with mixtures of both. Exemplary sources include tires from passenger cars, light trucks, or combinations of both. In certain embodiments of the first- third embodiments where ground, cured rubber is utilized, the ground, cured rubber is free of carbon black filler (i.e., the ground, cured rubber contains less than 1 phr carbon black filler or even 0 phr carbon black filler).

[0086] When at least one filler is utilized in the actinic radiation curable polymeric mixture, the total amount utilized may vary widely. Generally, the total amount of filler utilized will vary depending upon the type of filler and the properties sought in the cured polymeric mixture produced from the actinic radiation curable polymeric mixture. As well, in certain embodiments of the first-third embodiments, the amount of filler will also be adjusted based upon any viscosity increase that it causes to the overall actinic radiation curable polymeric mixture. I n certain embodiments of the first-third embodiments, the total amount of filler utilized in the actinic radiation curable polymeric mixture is an amount that does not cause the viscosity of the mixture to exceed about 10,000 cps (at 25 °C), preferably not exceeding about 5,000 cps (at 25 °C). In certain embodiments of the first-third embodiments disclosed herein, the at least one filler is present in a total amount (i.e, the total of amount of all fillers if more than one is present) of up to about 2/3 of the total volume (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2%, or 1%) of the actinic radiation curable polymeric mixture. In certain embodiments of the first-third embodiments disclosed herein, the at least one filler is present in a total amount (i.e, the total of amount of all fillers if more than one is present) of about 40 to about 80 parts (based upon 100 total parts of (a) and (b)). I n certain embodiments of the first-third embodiments disclosed herein, the only fillers utilized are non-carbon black fillers and the total amount of all non-carbon black fillers (i.e, the total of amount of all non-carbon black fillers if more than one is present) is of up to about 2/3 of the total volume (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2%, or 1%) of the actinic radiation curable polymeric mixture. In certain embodiments of the first-third embodiments disclosed herein, the only fillers utilized are non-carbon black fillers and the total amount of all non-carbon black fillers (i.e, the total of amount of all non-carbon black fillers if more than one is present) is about 40 to about 80 parts (based upon 100 total parts of (a) and (b)). [0087] In certain embodiments of the first-third embodiments, at least one carbon black filler is utilized; in such embodiments the at least one carbon black filler may be utilized as the only filler but may alternatively be utilized in combination with one or more non-carbon black filler such as those discussed above. In those embodiments of the first-third embodiments disclosed herein that include at least one carbon black filler, the total amount of carbon black filler can vary and may include amounts such as at least 0.01 parts, 0.01 to less than 1 part, 0.05 to 0.5 parts (based upon 100 total parts of (a) and (b)).

[0088] In those embodiments of the first-third embodiments where at least one carbon black is utilized as a filler, various carbon blacks can be utilized. In certain embodiments of the first-third embodiments, one or more reinforcing carbon blacks are utilized. In other embodiments of the first-third embodiments, one or more non-reinforcing carbon blacks are utilized. In yet other embodiments of the first-third embodiments, at least one reinforcing carbon black is used in combination with at least one non-reinforcing carbon black. Carbon blacks having a nitrogen surface area of greater than 30 m ² /g and a DBP absorption of greater than 60 cm ³ /100 g) are referred to herein as "reinforcing carbon blacks" and carbon blacks having a lower nitrogen surface area and/or lower DBP absorption are referred to herein as "non-reinforcing carbon blacks." The nitrogen surface area and the DBP absorption provide respective characterizations of the particle size and structure of the carbon black. The nitrogen surface area is a conventional way of measuring the surface area of carbon black. Specifically, the nitrogen surface area is a measurement of the amount of nitrogen which can be absorbed into a given mass of carbon black. Preferably, the nitrogen surface area for carbon black fillers is determined according to ASTM test D6556 or D3037. The DBP absorption is a measure of the relative structure of carbon black determined by the amount of DBP a given mass of carbon black can absorb before reaching a specified viscous paste. Preferably, the DBP absorption for carbon black fillers is determined according to ASTM test D2414. Among the useful carbon blacks are furnace black, channel blacks, and lamp blacks. More specifically, examples of useful carbon blacks include super abrasion furnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace (FF) blacks, intermediate super abrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks, medium processing channel blacks, hard processing channel blacks and conducting channel blacks. Exemplary reinforcing carbon blacks include: N-110, N-220, N-339, N-330, N-351, N-550, and N-660, and combinations thereof. Exemplary non-reinforcing carbon blacks include: thermal blacks or the N9 series carbon blacks (also referred to as the N-900 series), such as those with the ASTM designation N- 907, N-908, N-990, and N-991.

Processes For Producing A Cured Polymeric Product

[0089] As discussed above, the third embodiment disclosed herein is directed to a process for producing a cured polymeric product. The process comprises: providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure having an atmosphere inside, an interior tank capable of containing a liquid mixture and having an atmosphere above the tank, and an interior support structure; providing to the interior tank a liquid actinic radiation curable polymeric mixture comprising: (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P] [F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; (iii) at least one actinic radiation sensitive photoinitiator; (iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinker reactive with F; repeatedly forming upon the interior support structure a layer from the liquid mixture; using actinic radiation to cure each layer, thereby producing a cured polymeric product. According to the third embodiment, at least one of the following has an oxygen level of less than 50 ppm (e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30 ppm, 25 ppm, 20 ppm, 15 ppm, 10 ppm, 5 ppm, 1 ppm, or less), including: the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere surrounding the interior support structure, or the atmosphere inside the exterior support structure; in certain such embodiments, the oxygen level of at least one of the foregoing has an oxygen level of less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm. In certain embodiments of the third embodiment, an additive manufacturing cartridge according to the first embodiment disclosed herein is utilized in the process. The processes of the third embodiment should be understood to include the use of an additive manufacturing cartridge according to the first embodiment (including all of the variations thereto, as described above, as if fully set forth herein). I n certain embodiments of the third embodiment, the liquid actinic radiation curable polymeric mixture is provided in a cartridge having an oxygen impermeable layer surrounding the liquid actinic radiation curable polymeric mixture.

[0090] I n certain embodiments of the third embodiment, the process further comprises adding an inert gas to at least one of: (a) the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank of the additive manufacturing device; (b) the atmosphere surrounding the interior support structure of the additive manufacturing device; or (c) the atmosphere inside the exterior support structure. Various inert gases such as nitrogen, argon, helium, carbon dioxide, and combinations thereof may be utilized in various embodiments of the processes of the third embodiment. I n certain embodiments of the third embodiment the inert gas comprises nitrogen. I n certain embodiments of the third embodiment, the process further comprises continuous addition of an inert gas to at least one of (a), (b), or (c), as discussed above, during the process of repeatedly forming layers from the liquid mixture and until a cured polymeric product has been produced. I n certain embodiments of the third embodiment wherein the process includes the use of a cartridge (i.e., an actinic radiation manufacturing cartridge), the process further comprises adding an inert gas (e.g, as discussed above) to the cartridge to facilitate providing of the liquid actinic radiation curable polymeric mixture to the interior tank. I n certain embodiments of the third embodiment wherein the process includes the use of a cartridge (i.e., an actinic radiation manufacturing cartridge), the process further comprises removing gas from the cartridge (e.g., gas that may have been intentionally included with the contents of the cartridge and/or gas that may have entered the cartridge during storage or shipping) and supplying inert gas to the cartridge as the liquid actinic radiation curable polymeric mixture is removed during forming.

[0091] I n certain embodiments of the third embodiment, the cartridge utilized in the process comprises at least two separate compartments, as discussed in more detail above.

[0092] As discussed above, the third embodiment disclosed herein is directed to a process for producing a cured polymeric product. This process comprises providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure, an interior tank capable of containing a liquid mixture, and an interior support structure; providing a liquid mixture comprising an actinic radiation curable polymeric mixture according to the first embodiments disclosed herein (i.e., as previously described) to the interior tank; repeatedly forming upon a support structure a layer from the liquid mixture; using actinic radiation to cure each layer; thereby producing a cured polymeric product. According to the third embodiment disclosed herein, various types of additive manufacturing devices may be utilized. Generally, a great variety of additive manufactures devices are commercially available from companies including, but not limited to, 3D Systems, Inc. (Rock Hill, South Carolina) and Stratasys Ltd. (Eden Prairie, Minnesota). I n certain embodiments, the additive manufacturing device forms the product by a process that comprises solidifying each layer by using the actinic radiation to trace a pattern in the liquid material; in certain such embodiments the device contains no printer head; in certain such embodiments, such a process can be referred to as vat photopolymerization. In certain embodiments of the third embodiment, the additive manufacturing device forms the product by a process that comprises solidifying each layer by using actinic radiation to provide at least one pattern on the liquid material, such a process can be referred to as laser rastering. In certain embodiments of the third embodiment, the laser rastering can be understood as involving the use of pinpoint radiation which is moved across the service to result in an overall pattern being provided. In certain embodiments of the third embodiment, the additive manufacturing device forms the product by a process that comprises solidifying each layer by using actinic radiation to project at least one image on the liquid material, such a process can be referred to as digital light processing. As used herein, the phrase tracing a pattern in the liquid material is intended to encompass both digital light processing and laser rastering processes. In other embodiments, the additive manufacturing device forms the product by dispensing the mixture from a printing head having a set of nozzles; in certain such embodiments, such a process can be referred to as material jetting.

[0093] According to the process of the third embodiment, the thickness of each layer that is formed by the additive manufacturing device (e.g., upon the support structure) may vary. I n certain em bodiments, each layer has a thickness of about 0.01 mm to about 1 mm, including a thickness of 0.01 mm to 1 mm, about 0.1 m m to about 0.3 mm, and 0.1 mm to 0.3 mm. According to the third embodiment, the materials of construction for the support structure of the additive manufacturing device upon which the product is formed may vary. In certain embodiments of the third embodiment, the support structure comprises polysiloxane polymer (e.g., polydimethylsiloxane or PDMS), a halogenated polymer coating, a halogenated wax coating, or a combination thereof. Non-limiting examples of halogenated polymer coatings include fluorinated halogenated polymers such as polytetrafluoroethylene (PTFE, sold under the tradename Teflon® by DuPont). Non-limiting examples of halogenated wax coatings include fluorinated waxes, chlorinated waxes, brominated waxes, and combinations thereof. Various commercial sources for halogenated waxes exist such as Dover Chemical Corporation (Dover, Ohio) which sells Doverguard® brand brominated waxes and Chlorez® brand chlorinated waxes. Use of the foregoing materials of construction for the support structure or employing those materials as a coating for the support structure upon which the product is formed can facilitate the processes of the third embodiment and production of the resulting products by enabling the product to be more easily removed from the support structure, preferably without curing or otherwise sticking to the support structure such that removal therefrom involves tearing or breaking one or more layers of the product. As those of skill in the art will appreciate, the particular material of construction used for the support structure may be intentionally varied depending upon the ingredients contained in the actinic radiation curable polymeric mixture (in particular, the type of chain extender utilized).

[0094] The wavelength of the actinic radiation used in the processes of the third embodiment disclosed herein may vary, depending upon the particular type of additive manufacturing device chosen or the setting chosen for a particular additive manufacturing devices (some devices allow the user to select different wavelength ranges). In certain embodiments, the actinic radiation has a wavelength in the UV to Visible range. In certain embodiments, the actinic radiation (light) has a wavelength of about 320 to less than 500 nm, including about 350 to about 450 nm, and about 365 to about 405 nm.

[0095] In certain embodiments of the processes of the third embodiment disclosed herein, the process includes the use of a cartridge to provide the liquid mixture comprising the actinic radiation curable polymeric mixture. In certain embodiments of the processes of the third embodiment disclosed herein, the interior tank of the additive manufacturing device further comprises a component capable of receiving a liquid mixture from at least one cartridge. In other words, in such embodiments, the interior tank of the additive manufacturing device is capable of receiving a liquid mixture from at least one cartridge.

[0096] Various combinations of one or more cartridges to contain the ingredients of the actinic radiation curable polymeric mixture in its various sub-embodiments (as described above) are envisioned for use in certain embodiments of the processes of the third embodiment. In certain embodiments of the third embodiment, the process comprises the use of at least two cartridges, with one cartridge comprising: the polyfunctionalized diene monomer-containing polymer having the formula [P][F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different and chain extender based upon F or reactive with F and the second cartridge comprising chain extender based upon F or reactive with F along with at least one of an actinic radiation sensitive photoinitiator and a photosensitizer. In certain of the foregoing embodiments, the second cartridge further comprises a crosslinker reactive with F; alternatively, a third cartridge comprising a crosslinker reactive with F can be provided.

Cured elastomeric/polymeric product or article

[0097] As discussed above, the third embodiment disclosed herein is directed to a process for producing a cured polymeric product. Additionally, the cartridges of the first embodiment (and the cartridges made using the process of the second embodiment) can be used to produce a cured polymeric product. In certain embodiments of the first-third embodiments, the cured polymeric product comprises a crosslinked polyfunctionalized diene polymer comprising a diene polymer chain backbone [P], multiple functional groups F where each F is the same or different, and crosslinkages between pairs of functional groups. In other embodiments of the first-third embodiments, the cured polymeric product can be understood as comprising a cured version of the actinic radiation curable polymeric mixture as previously described. [0098] I n certain embodiments of the first-third embodiments, the cured polymeric product comprises an elastomeric polymeric product. I n certain embodiments of the first-third embodiments, the cured polymeric product is elastomeric. As used herein, the term elastomeric can be understood according to the following explanation. Yield as used herein refers to the onset of plastic deformation in a material under an applied load. Plastic deformation is deformation that remains after the load is removed. The yield point is the peak in a load-elongation curve (load on y axis, elongation on x axis) at which plastic flow becomes dominant. Thus, as used herein, the term elastomer or elastomeric refers to a material which does not exhibit any definite yield point or area of plastic deformation; in other words, the deformation of an elastomeric material remains elastic as opposed to becoming plastic.

[0099] I n certain embodiments of the first-third embodiments, the cured elastomeric product comprises crosslinkages which contain no sulfur. I n certain embodiments of the first- third embodiments, the cured elastomeric product comprises crosslinkages which are essentially free of sulfur. By essentially free of sulfur is meant that no more than about 1 ppm of sulfur in the overall actinic radiation curable polymeric mixture of the cured polymeric product, including less than 1 ppm, less than about 0.1 ppm, less than 0.1 ppm, and 0 ppm. I n certain embodiments of the first-third embodiments, the cured elastomer mixture comprises crosslinkages which contain sulfur, various amounts of which are possible.

Kits

[00100] I n certain embodiments of the first embodiment, one or more cartridges can be assembled into a kit (i.e., such a kit comprises at least two containers or cartridges as previously described). Such kits can be useful in producing a cured polymeric product by additive printing. For example, by the use of such kits, a manufacturer may utilize different types and combinations of polyfunctionalized diene monomer-containing polymer(s), chain extender(s), photoinitiator(s), photosensitizer(s), and crosslinker(s). The use of a kit with multiple cartridges or could provide an advantage in material jetting processes where the machine and print head could be used to selectively dispense the materials from different cartridges or containers without the need to pre-mix the materials. Use of a kit comprising at least one cartridge or container with at least one filler would allow for the filler to be in a stable dispersion and mixed (as needed) with the other components either just prior to or upon printing. I n certain embodiments, the kit comprises at least two cartridges (or a cartridge with at least two compartments), wherein at least one ca rtridge (or compartment) comprises a polyfunctionalized diene monomer-containing polymer having the formula [P] [F] _n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different and a chain extender based upon F or compatible with F; and at least a second cartridge (or compartment) comprises a chain extender based upon F or compatible with F, at least one of an actinic radiation sensitive photoinitiator and a photosensitizer, and optionally a crosslinker reactive with F. I n certain of the foregoing embodiments of the kit, at least one cartridge (or compartment) further comprises at least one metal or metal oxide filler. In certain of the foregoing em bodiments of the kit, at least cartridge (or compartment) further comprises at least one filler (as discussed above). The particular ingredients of each cartridge (or compartment) used in a kit can vary in conjunction with the description of the actinic radiation curable polymeric mixture as previously described.

Rubber goods

[00101] As discussed above, according to the fourth embodiment disclosed herein, a rubber good that is made from (i.e., comprises) a cured polymeric product resulting from the process of the third embodiment disclosed herein (as described above) is disclosed. As mentioned above, descriptions of the ingredients of the actinic radiation curable polymeric mixture (and resulting cured polymeric product) apply to the fullest extent possible to certain embodiments of the fourth embodiment, as if fully set forth with specific language directed to the cured polymeric mixture of the fourth embodiment.

[00102] I n certain embodiments of the fourth embodiment, the rubber good comprising the cured polymeric product comprises at least one of: a bushing, a seal, a gasket, a conveyor belt, a hose, or a glove (or gloves). I n certain embodiments of the fourth embodiment, the rubber good comprises a bushing. I n certain embodiments of the fourth embodiment, the rubber good comprises a seal. In certain embodiments of the fourth embodiment, the rubber good comprises a gasket. In certain embodiments of the fourth embodiment, the rubber good comprises a conveyor belt. I n certain embodiments of the fourth embodiment, the rubber good comprises a hose. In certain embodiments of the fourth embodiment, the rubber good comprises a glove or gloves.

[00103] Manufacturing rubber goods (e.g., bushings, seals, gaskets, conveyor belts, hoses, or gloves) by an additive manufacturing process using the actinic radiation curable polymeric mixtures disclosed herein or according to the processes of the third embodiment disclosed herein can provide an advantage in terms of being able to produce shapes and designs that cannot be produced using traditional manufacturing processes such as molding. As a non-limiting example a hose manufactured by an additive manufacturing process using the actinic radiation curable polymeric mixtures disclosed herein or according to the processes of the third embodiment disclosed herein could include internal structure(s) such as multiple channels (to allow separate passage of ingredients through a portion of the hose) or internal projections, protrusions or other internal structure(s) to effect mixing of ingredients during flow through the hose. Another non-limiting example includes the ability to manufacture custom- fitting or custom sized gloves without the need for production of a custom form or a multitude of forms in different sizes.

[00104] I n certain embodiments of the fourth embodiment, the rubber good comprises a tire. In certain embodiments of the fourth embodiment, the rubber good comprises a tire having at least one component comprised of a cured polymeric product (e.g., resulting from the processes of the third embodiment or from use of the cartridge according to the first embodiment). In certain such embodiments, the com ponent of the tire comprises at least one of: a tread, a bead, a sidewall, an innerliner, and a subtread. In certain embodiments of the fourth embodiment, the component of the tire comprises a tire tread. In certain embodiments of the fourth embodiment, the component of the tire comprises a subtread. I n certain embodiments of the fourth embodiment, the component of the tire comprises a tire sidewall. I n certain embodiments of the fourth embodiment, the component of the tire comprises a tire bead. In certain embodiments of the fourth embodiment, the component of the tire comprises a tire innerliner.

[00105] Manufacturing a tire component (e.g., treads, beads, sidewalls, innerliners or subtreads) by an additive manufacturing process using the actinic radiation curable polymeric mixtures disclosed herein or according to the processes of the third embodiment disclosed herein can provide an advantage in terms of being able to produce shapes and design that cannot be produced using traditional manufacturing processes such as molding. As a non-limiting example, in certain embodiments of the fourth embodiment, wherein the at least one component of the tire comprises a tread, a tread can be produced that includes at least one of the following: a closed hollow void, an undercut void, and an overhung void. As used herein, the phrase "closed hollow void" refers to a void that is not open to the road-contacting surface of the tread (at least not upon manufacture); the particular shape of the closed hollow is not particularly limited and shapes that are circular, elliptical, square, rectangular, trapezoidal, rectangular, and triangular may be utilized in various embodiments. Non-limiting examples of closed hollow voids are provided in Figure 1. As used herein, the phrase "overhung void" refers to a void that is partially open to the road-contacting surface of the tread (upon manufacture), that is wider (in at least one dimension) than the opening, and that includes upper walls (at the road-contacting surface) having a thickness less than the overall depth of the void and projecting over and partially covering the opening to the road- contacting surface of the tread. Non-limiting examples of overhung voids are provided in Figure 2. As used herein, the phrase "undercut void" refers to a void that is partially open to the road-contacting surface of the tread (upon manufacture), that is wider (in at least one dimension) than the opening, and that includes upper walls (at the road-contacting surface) that partially extend into the void without hanging over the void. In certain embodiments, the undercut void has unsupported walls angled (from the bottom towards the top) generally toward the opening to the road-contacting surface. In certain embodiments, the overhung void has unsupported walls that are substantially parallel (+ or - about 5°) to the road-contacting surface or have angles (from the bottom towards the top) generally directed away from the opening to the road-contacting surface. Non-limiting examples of overhung voids are provided in Figure 3.

[00106] To the extent that the term "includes" or "including" is used in the specification or the claims, it is intended to be inclusive in a manner similar to the term "comprising" as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term "or" is employed (e.g., A or B) it is intended to mean "A or B or both." When the applicants intend to indicate "only A or B but not both" then the term "only A or B but not both" will be employed. Thus, use of the term "or" herein is the inclusive, and not the exclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995). Also, to the extent that the terms "in" or "into" are used in the specification or the claims, it is intended to additionally mean "on" or "onto." Furthermore, to the extent the term "connect" is used in the specification or claims, it is intended to mean not only "directly connected to," but also "indirectly connected to" such as connected through another component or components.

[00107] While the present application has been illustrated by the description of embodiments thereof, and while the embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. Therefore, the application, in its broader aspects, is not limited to the specific details and embodiments described. Accordingly, departures may be made from such details without departing from the spirit or scope of the applicant's general inventive concept.

[00108] This application discloses several numerical range limitations that support any range within the disclosed numerical ranges even though a precise range limitation is not stated verbatim in the specification because the embodiments could be practiced throughout the disclosed numerical ranges. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity. As well, all numerical limitations and ranges that are preceded by the word "about" should be understood to include the particular number or range without the about as if fully set forth herein.